studies on the reactive species in fluoride-mediated ... supporting information studies on the...

S-1

Supporting Information

Studies on the Reactive Species in Fluoride-Mediated Carbon-Carbon Bond Forming

Reactions: Carbanion F ormation by Desilylation with Fluoride and Enolates

Margaret M. Biddle and Hans J. Reich,*

Department of Chemistry, University of Wisconsin

1101 University Avenue

Madison, Wisconsin 53706

[email protected]

Contents

ExperimentalGeneral . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-3

Starting MaterialsPreparation of Sulfides - Sample Procedure: Benzyl 2-Pyridyl sulfide (1b-H) . . . . . . . . . . . . . . . . . . . . S-3Benzyl N-methyl-2-imidazolyl Sulfide (1c-H) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-3Preparation of Silanes - Sample Procedure: "-Trimethylsilylbenzyl Phenyl Sulfide (1a-Si) . . . . . . . . . . . . . . . . . .-3"-(Dimethylphenylsilyl)benzyl Phenyl Sulfide (1a-Si, R = Ph) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-3"-(Dimethylisopropylsilyl)benzyl Phenyl Sulfide(1a-Si, R = iPr) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-4"-(Trimethylsilyl)benzyl 2-Pyridyl Sulfide (1b-Si) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-4"-(Trimethylsilyl)benzyl N-Methyl-2-imidazolyl Sulfide (1c-Si). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-41-(Trimethylsilyl)allyl Phenyl Sulfide (4a-Si). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-41-(Trimethylsilyl)allyl 2-Pyridyl Sulfide (4b-Si) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-41-(Phenylthio)-1-trimethylsilyl-2-butyne (9-Si). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-4

Low Temperature Multinuclear NMR SpectroscopyGeneral . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-5Sample Preparation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-5HMPA Titration of "-(Phenylthio)benzyllithium (1a-Li) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-5Variable Temperature NMR experiment of 1a-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-6DMPU Titration of 1a-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-7Crypt Titration of 1a-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-7HMPA Titration of "-(2-Pyridylthio)benzyllithium (1b-Li). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-8Variable Temperature NMR experiment of "-(N-Methyl-2-imidazolylthio)benzyllithium (1c-Li) . . . . . S-9HMPA Titration of 1c-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-9DMPU Titration of 1c-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-10Crypt solvated 1c-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-10Variable Temperature NMR Experiment of 1-(Phenylthio)allyllithium (4a-Li). . . . . . . . . . . . . . . . . . . . S-11HMPA Titration of 4a-Li. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-12HMPA Titration of 1-(2-Pyridylthio)allyllithium (4b-Li). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-12

Reactions with Cyclohexenone1-("-Phenylthiobenzyl)]-2-cyclohexen-1-ol (2a-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-133-("-Phenylthiobenzyl)cyclohexanone (3a-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-131-("-[2-Pyridylthio]benzyl)-2-cyclohexen-1-ol (2b-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-133-("-[2-Pyridylthio]benzyl)cyclohexanone (3b-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-131-("-[N-Methyl-2-imidazolylthio]benzyl)-2-cyclohexen-1-ol (2c-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-133-("-[N-Methyl-2-imidazolylthio]benzyl)cyclohexanone (3c-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-13

S-2

SPh

M

S

M N

Ph S

M N

1b-M

4a-M 4b-M

N

N

S Ph

M

1c-M

PhS Ph

M

1a-M

Me3Si

S

SMe3Si

S

SSPh

SiMe3

SPh

SiMe3

HOHOSAr

O

SAr

OSAr

ArS

5-H 6-H 7-H 8-H

11-Si9-Si

2-M 3-M

O

SAr

Ph

SAr

Ph

M+ O M+

10-Si 12-Si

3-H SAr

Ph

O

Ara Ph

b 2-Py

c 2-Im

1-(1-[Phenylthio]allyl)cyclohex-2-enol (5a-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-133-(1-[Phenylthio]allyl)cyclohexanone (7a-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-141-(1-[2-Pyridylthio]allyl)cyclohex-2-enol (5b-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-143-(1-[2-Pyridylthio]allyl)cyclohexanone (7b-H). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .-14

Catalytic Cycle StudiesReaction of Tributylsilyl Fluoride and n-BuLi in the Presence of HMPA. . . . . . . . . . . . . . . . . . . . . . . . . S-16Reaction of Triphenylsilyl Fluoride and PhLi in the Presence of HMPA. . . . . . . . . . . . . . . . . . . . . . . . . S-16Reaction of 1a-Si with TBAF. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-17Reaction of 1a-Si with TASF. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-17Reaction of 1a-Si with TBAT. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-17Reaction of Crypt-Solvated "-(Phenylthio)benzyllithium with Trimethylsilyl Fluoride. . . . . . . . . . . . . . S-18Check for Proton Transfer of 1a-Si. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-19Reaction of Crypt-Solvated Lithium Enolate of Cyclohexanone with TMSF. . . . . . . . . . . . . . . . . . . . . . S-20Reaction of Crypt Solvated Lithium Enolate of Cyclohexanone with 1a-Si. . . . . . . . . . . . . . . . . . . . . . . S-21Reaction of HMPA Solvated Lithium Enolate with Silane 1a-Si. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-22Catalytic cycle with HMPA. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-22

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-23Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . S-24

S-3

ExperimentalGeneral. Tetrahydrofuran and diethyl ether were freshly distilled from sodium benzophenone ketyl before use.

Dimethyl ether was purified by condensing several mL into an oven-dried, N2 flushed graduated centrifuge tube anddried with 0.5 mL of n-BuLi, then distilling the dimethyl ether by cannula into the reaction vessel. Hexamethylphosphoramide (HMPA) and N,N’-dimethylpropylene urea (DMPU) were distilled from calcium hydrideat reduced pressure and stored under nitrogen atmosphere over 4Å molecular sieves. Crypt[2.1.1] was warmed to ca.40 °C if used neat or used as a 1.8 M solution in THF. All glassware was placed in an oven at 110 °C overnight orflame-dried prior to use. n-BuLi was titrated with n-propanol in THF at -78 °C with 1,10-phenanthroline as anindicator.[S-1] Tetrabutylammonium fluoride (TBAF) solutions were made from the solid hydrate dissolved in THFand dried over 4Å molecular sieves for 5-15 minutes prior to use.

Starting Materials Commercially available material were used, except for tributylsilyl fluoride,[S-2] benzyl phenyl sulfide (1a-H),[S-3]

allyl phenyl sulfide (4a-H),[S-4] allyl 2-pyridyl sulfide(4b-H),[S-5] tetrabutylammonium difluorotriphenylsilicate(TBAT),[S-6] 3-methyl-1-(1,3-dithan-2-yl)-1-trimethylsilylpropene (10-Si, 1H NMR (300 MHz, CDCl3), * 5.49 (sept,J = 1.5 Hz, 1H), 3.07 (m, 2H), 2.51 (dt, J = 14, 4 Hz, 2H), 2.0 (m, 2 H), 1.98 (d, J = 1.5 Hz, 3H), 1.82 (d, J = 1.5 Hz,3H), 0.16 (s, 9H)),[S-7] trimethyl-(2-vinyl-[1,3]dithian-2-yl)-silane (11-Si, 1H NMR (300 MHz, CDCl3), * 5.94 (dd, J= 17, 10 Hz, 1H), 5.37 (dd, J = 17, 2 Hz, 1H), 5.34 (dd, J = 10, 2 Hz, 1H), 3.05-2.95 (m, 2H), 2.87-2.82 (m, 2H),2.39 (dt, J = 14, 4 Hz, 2 H), 0.13 (s, 9H),[S-8] 3-phenylthio-3-trimethylsilyl-2-methylpropene (12-Si, 1H NMR (300MHz, CDCl3), * 7.35-7.24 (m, 5H), 4.81 (m, 2H), 3.35 (s,1H), 1.82 (t, J = 1.5 Hz, 3H), 0.21 (s, 9H)),[S-9] which wereprepared by standard or literature procedures.

Preparation of Sulfides - Sample Procedure: Benzyl 2-Pyridyl sulfide (1b-H). 2-Mercaptopyridine (412 mg,3.7 mmol), benzyl bromide (440 :L, 3.7 mmol), 5 mL of CH3CN and triethylamine (570 :L, 4.1 mmol) were addedto a 10 mL RBF. The solution turned orange-green with a white precipitate and stirred 2 h, and was taken up in 1:1hexanes/ether (100 mL), washed 1 x NaHCO3 (50 mL), 2 x H2O (50 mL), 1 x brine (50 mL), dried MgSO4, filtered,rotary evaporated to yield 0.623 g (83.7%). 1H NMR (300 MHz, CDCl3), * 8.45 (ddd, J = 5, 2, 1 Hz, 1H), 7.46(ddd, J = 8, 7, 1 Hz, 1H), 7.41-7.26 (m, 5H), 7.15 (dd, J = 8, 1 Hz, 1H), 6.96 (ddd, J = 7, 5, 1 Hz, 1H), 4.44 (s,2H). 13C NMR (75.4 MHz, CDCl3), *158.7 (C), 149.3 (CH), 137.9 (C), 135.9 (CH), 128.9 (CH), 128.4 (CH), 127.0 (CH),122.0 (CH), 119.5 (CH), 34.3 (CH2). HRMS (EI) (m/z): calcd. for C12H11NS [M]+ 201.0612; found 201.0604.

Benzyl N-methyl-2-imidazolyl Sulfide (1c-H). Prepared according to standard procedure for making sulfidesfrom 408 mg of 2-mercapto-N-methyl-imidazole (3.6 mmol), 430 :L of benzyl bromide (3.6 mmol) and 550 :L of triethylamine (3.9 mmol), stirred 2 h to yield 619 mg (84.1%). 1H NMR (300 MHz, CDCl3), * 7.25-7.23 (m, 3H),7.13-7.10 (m, 3H), 6.86 (d, J = 1 Hz, 1H), 4.15 (s, 2 H), 3.23 (s, 3H). 13C NMR (75.4 MHz, CDCl3), * 140.4 (C),137.8 (C), 129.6 (CH), 128.6 (CH), 128.4 (CH), 119.5 (CH), 127.3 (CH), 122.4 (CH), 40.3 (CH3), 33.0 (CH2). HRMS (EI) (m/z): calcd. for C11H12N2S (M+) 204.0721; found 204.0727.

Preparation of Silanes - Sample Procedure: "-Trimethylsilylbenzyl Phenyl Sulfide (1a-Si). Benzyl phenylsulfide (998 mg, 5.0 mmol) was added to a 50 mL RBF, purged with nitrogen, and 25 mL THF is added. This wascooled to -78 °C and metalated with n-BuLi (2.15 mL, 2.35 M, 5.05 mmol). Trimethylsilyl chloride (1.26 mL, 10.0mmol) was added and stirred 20 min and allowed to warm to RT. Triethylamine (1.4 mL, 10.0 mmol) was added,the solution was taken up in 1:1 hexanes/ether (200 mL), washed 1 x NaHCO3 (1000 mL), 2 x H2O (1000 mL), 1 xbrine (100 mL), dried MgSO4, filtered, rotary evaporated. 1H NMR (300 MHz, CDCl3), * 7.31-6.98 (m, 10H), 3.75(s, 1H), 0.10 (s, 9H). 13C NMR (75.4 MHz, CDCl3), *141.1 (C), 138.2 (C), 128.5 (CH), 128.2 (CH), 127.9 (CH),127.5 (CH), 125.4 (CH), 125.2 (CH), 41.0 (CH), -2.61 (CH3). HRMS (EI) (m/z): calcd. for C16H20SSi, [M]+

272.1055; found 272.1064.

"-(Dimethylphenylsilyl)benzyl Phenyl Sulfide (1a-Si, R = Ph). Prepared according to standard procedure formaking silanes from 399 mg of benzyl phenyl sulfide (2.0 mmol), 870 :L of n-BuLi (2.53 M, 2.0 mmol), 500 :L ofdimethylphenylsilyl chloride (3.0 mmol), stirred 1 h. 1H NMR (300 MHz, CDCl3), * 7.47-7.31 (m, 5H), 7.18-7.00(m, 10H), 3.92 (s, 1H), 0.43 (s, 3H), 0.34 (s, 3H). 13C NMR (75.4 MHz, CDCl3), *140.5 (C), 138.0 (C), 135.7 (C),134.3 (CH), 129.5 (CH), 128.5 (CH),128.0 (CH), 127.9 (CH), 127.8 (CH), 127.6 (CH), 125.5 (CH), 125.3 (CH),40.7 (CH), -3.9 (CH3), -4.4 (CH3). HRMS (EI) (m/z): calcd. for C21H22SSi [M]+ 334.1212; found 334.1201.

"-(Dimethylisopropylsilyl)benzyl Phenyl Sulfide(1a-Si, R = iPr). Prepared according to standard procedurefor making silanes from 399 mg of benzyl phenyl sulfide (2.0 mmol), 870 :L of n-BuLi (2.53 M, 2.0 mmol), 470:L of dimethylphenylsilyl chloride (3.0 mmol), stirred 1 h. 1H NMR (300 MHz, CDCl3), * 7.39-7.09 (m, 10H),3.89 (s, 1H), 1.05 (s, 6H), 1.04 (m, 1H), 0.12 (s, 3H), -0.07 (s, 3H). 13C NMR (75.4 MHz, CDCl3), * 141.0 (C),138.2 (C), 128.5 (CH), 128.2 (CH), 128.0 (CH), 127.7 (CH), 125.4 (CH), 125.3 (CH), 39.0 (CH), 17.6 (CH3), 12.3(CH), -6.6 (CH3). HRMS (EI) (m/z): calcd. for C18H24SSi [M]+ 300.1368; found 300.1356.

S-4

"-(Trimethylsilyl)benzyl 2-Pyridyl Sulfide (1b-Si). Prepared according to standard procedure for makingsilanes from 302 mg of benzyl-2-pyridyl sulfide (1.5 mmol), 660 :L of n-BuLi (2.53 M, 1.65 mmol), 230 :L oftrimethylsilyl chloride (1.8 mmol), stirred 1 h to yield 0.277 g (67.4%). 1H NMR (300 MHz, CDCl3), * 8.34 (ddd, J= 5, 2, 1 Hz, 1H), 7.35-7.22 (m, 5H), 7.11 (dt, J = 7, 1 Hz, 1H), 7.05 (dt, J = 7, 1 Hz, 1H), 6.87 (ddd, J = 7, 5, 1 Hz),4.29 (1H, s), 0.11 (9H, s). 13C NMR (75.4 MHz, CDCl3), * 160.3 (C), 149.5 (CH), 141.8 (C), 136.2 (CH), 128.3(CH), 128.0 (CH), 125.7 (CH), 121.9 (CH), 119.5 (CH), 37.5 (CH), -2.3 (CH3). HRMS (EI) (m/z): calcd. forC15H19NSSi, [M]+ 273.1007; found 273.0997.

"-(Trimethylsilyl)benzyl N-Methyl-2-imidazolyl Sulfide (1c-Si). Prepared according to standard procedure formaking silanes from 307 mg of benzyl N-methyl-2-imidazolyl sulfide (1.5 mmol), 660 :L of n-BuLi (2.53 M, 1.65mmol), 230 :L of trimethylsilyl chloride (1.8 mmol), stirred 10 min to yield 0.414 g (99.8%). 1H NMR (300 MHz,CDCl3), * 7.27-7.17 (m, 5H), 6.99 (d, J = 1 Hz, 1H), 6.74 (d, J = 1 Hz, 1H), 3.98 (s, 1H), 3.33 (s, 3H), 0.13 (s, 9H). 13C NMR (75.4 MHz, CDCl3), * 141.9 (C), 141.7 (C), 129.5 (CH), 128.0 (CH), 127.9 (CH), 125.7 (CH), 122.1(CH), 43.4 (CH), 33.1 (CH3), -2.5 (CH3). HRMS (EI) (m/z): calcd. for C14H20N2SSi (M+), 276.116; found 276.1103.

1-(Trimethylsilyl)allyl Phenyl Sulfide (4a-Si). Prepared according to standard procedure for making silanesfrom 150 mg of phenyl allyl sulfide (1.0 mmol), 440 :L of n-BuLi (2.53 M, 1.1 mmol), 200 :L of trimethylsilylchloride (1.5 mmol), stirred 1 h to yield 222 mg (100%). 1H NMR (300 MHz, CDCl3), * 7.32-7.13 (m, 5H), 5.76(ddd, J = 17, 10, 9 Hz, 1H), 5.02 (dt, J = 17, 1 Hz, 1H), 4.95 (dq, J = 10, 1 Hz, 1H), 3.26 (d, J = 9 Hz, 1H), 0.162 (9H, s). 13C NMR (75.4 MHz, CDCl3), * 137.4 (C), 136.9 (CH), 128.8 (CH), 128.5 (CH), 125.5 (CH), 114.1 (CH2),39.3 (CH), -2.9 (CH3). HRMS (EI) (m/z): calcd. for C12H18SSi [M]+, 222.0899; found 222.0904.

1-(Trimethylsilyl)allyl 2-Pyridyl Sulfide (4b-Si). Prepared according to standard procedure for making silanesfrom 151 mg of allyl 2-pyridyl sulfide (1.0 mmol), 420 :L of n-BuLi (2.53 M, 1.05 mmol), 140 :L of trimethylsilylchloride (1.1 mmol), stirred 10 min to yield 200 mg (89%). 1H NMR (300 MHz, CDCl3), * 8.43 (ddd, J = 6, 2, 1 Hz,1H), 7.49 (ddd, 1H), 7.21 (dt, J = 8, 1 Hz, 1H), 6.97 (ddd, J = 8, 6, 1 Hz, 1H), 5.87 (ddd, J = 17, 10, 1 Hz, 1H), 5.18(dt, 17, 1.5 Hz, 1H), 4.99 (ddd, J = 10, 1.5, 1, 1H), 3.76 (dt, J = 8, 1 Hz, 1H), 0.14 (9H, s). 13C NMR (75.4 MHz,CDCl3), * 159.9 (C), 149.4 (CH), 136.6 (CH), 135.9 (CH), 122.1 (CH), 119.4 (CH), 114.0 (CH2), 35.7 (CH), -2.9(CH3). HRMS (EI) (m/z): calcd. for C11H17NSSi (M+), 223.0851; found 223.0843.

1-(Phenylthio)-1-trimethylsilyl-2-butyne (9-Si). 1-(Phenylthio)but-2-yne [S-10] (487 mg, 3 mmol) was added to a25 mL RBF. This was charged with nitrogen, 12 mL of THF was added, cooled to -78 °C, and metalated with 1.35M LDA (2.7 mL, 3.6 mmol). The solution turned dark reddish black and after 15 min was quenched withtrimethylsilyl chloride (780 µL, 6 mmol), stirred 10 min and warmed to RT. The solution was taken up in 1:1hexanes/ether (100 mL), washed 1 x NaHCO3 (50 mL), 2 x H2O (50 mL), 1x brine (50 mL), dried MgSO4, filtered,and rotary evaporated to yield 667 mg of alkyne (< 3% of allene seen). 1H NMR (300 MHz, CDCl3), alkyne, * 7.47-7.26 (m, 5H), 3.22 (q, J = 2.5 Hz, 1H), 1.80 (d, J = 2.5 Hz, 3H), 0.23 (s, 9H). 13C NMR (75.4 MHz, CDCl3), * 137.6( C), 128.6 (CH) , 128.6 (CH), 125.7 (CH), 78.3 ( C), 77.55(C), 25.0 (CH), 3.8(CH3), -2.9(CH3). HRMS (EI-EMM)(m/z): calcd. for C13H17SSi (M+), 233.0820; found 233.0832.

S-5

Low Temperature Multinuclear NMR Spectroscopy

General. Low-temperature heteronuclear NMR experiments were performed on a 360 MHz spectrometer with a10 mm or 5 mm broadband probe at the following frequencies: 90.556 MHz (13C), 139.905 MHz (7Li); 145.785 MHz(31P); 338.827 MHz (19F). Spectra were obtained in undeuterated THF, ether or dimethyl ether or a combinationthereof with the spectrometer unlocked. These solvent combinations allowed for the cooling of samples to -155 °Cwithout freezing. 13C spectra were acquired with composite pulse decoupling (CPD) and referenced internally to theC-2 carbon of THF (* 67.96 ppm). Lorenzian multiplication (LB) was applied to 13C spectra. 7Li spectra werereferenced externally to 0.3M LiCl/MeOH standard (* 0.00 ppm). 31P spectra were referenced externally to 1.0 MPPh3/THF standard (* -6.00 ppm) or internally to free HMPA (* -26.40 ppm). Gaussian multiplication was appliedto 7Li and 31P spectra.

Sample Preparation. Samples were prepared in thin-walled 10 mm NMR tubes that were stored overnight undervacuum, fitted with 9 mm septa, wrapped with parafilm and purged with N2. Silicon grease was applied to the top ofthe septum to seal needle punctures. Samples were prepared and stored at -78 °C. For HMPA titrations, spectra ofthe active nuclei (13C, 7Li) were obtained at temperatures < -120 °C. The sample was removed, cooled in -78 °C, thegrease from the septum was removed and the desired amount of HMPA was added, and the septum was regreased,the sample was reinserted into the probe, the temperature was allowed to equilibrate and 13C, 7Li and 31P spectra wereobtained. For variable temperature experiments, temperature equilibration for 5-10 minutes was allowed beforespectra were obtained. Temperature was measured by console reading or use of tris(trimethylsilyl)methane as aninternal thermometer.[16g]

HMPA Titration of "-(Phenylthio)benzyllithium (1a-Li). Benzyl phenyl sulfide (62 mg, 0.31 mmol) wasadded to a dried 10 mm NMR tube. The tube was flushed with N2 and 2.5 mL of THF was added. The NMR tubewas cooled to !78 °C under positive N2 pressure, and 0.5 mL of Me2O dried with n-BuLi was condensed into thetube. The solution was metalated with n-BuLi (110 µL, 2.58 M). 13C and 7Li spectra were obtained at -115 °C. HMPA was added and 31P and 7Li spectra were obtained at -115 °C with 0.5, 1 equiv. of HMPA and cooled to -120°C for 2 and 4 equiv. of HMPA. The sample was quenched with propionic acid in ether (300 µL, 3 M). Spectra areshown in Figure 1 in text.

S-6

155 150

155 150

125 120 115 110 105

125 120 115 110 105ppm

(b) 6 equiv. HMPA

(a) 0 equiv. HMPALi

α1

6

3

4

5

2 S i

o m

p

1a-Li

-80 °C

-50 °C

-40 °C

-30 °C

-20 °C

-10 °C

10 °C

20 °C

-50 °C

-40 °C

-20 °C

10 °C

15 °C

25 °C

1 63 45 2i om p

1 63 45 2

i om p

Variable Temperature NMR experiment of 1a-Li. A 10 mm NMR sample was prepared according to standardprocedure from 60 mg of benzyl phenyl sulfide, 1.8 mL of THF and 1.2 mL of ether, and 120 µL n-BuLi (2.49 M) togive a yellow 0.10 M solution of lithium reagent. 13C spectra were obtained at -80 °C , -50 °C , -40 °C , -30 °C , -20°C , -10 °C , 10 °C and 20 °C until coalescence of the ortho and meta peaks was observed. HMPA (320 µL, 1.8mmol) was added and the solution turned copper-orange in color. 13C NMR spectra were obtained at -50 °C , -40°C, -20 °C , 10 °C , 15 °C and 25 °C. Coalescence of the ortho and meta peaks was not observed. Spectra areshown in Figure S-1.

Figure S-1. Variable temperature NMR experiment of 0.10 M 1a-Li in 3:2 THF/Et2O with 0 (a) and 6 (b) equiv. ofHMPA added.

S-7

155 150 0.5 0.0

0

4

8

Equiv.DMPU

7Li13C

DMPU

125 120 115 110 105ppm

N

NO

DMPU

Li

α1

6

3

4

5

2 S i

o m

p

1a-Li

1 63 45 2i om p

0 -1

Equiv.Crypt

7Li13C

2.0

1.0

0.5

0

155 150 145 140 135 130 125 120 115 110 105ppm

O O

NO

NO

Crypt

X

Li

α1

6

3

4

5

2 S i

o m

p

1a-Li

1 63 45 2i om p

X

DMPU Titration of 1a-Li. Benzyl phenyl sulfide (82 mg, 0.41 mmol) was added to a dried 10 mm NMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of Et2O was added. The NMR tube was cooled to!78 °C under positive N2 pressure. The solution was metalated with n-BuLi (370 µL, 1.12 M). 13C and 7Li NMRspectra were obtained at -110 °C . THF (2 mL) was added to prevent precipitation. DMPU was added and 13C and7Li spectra were obtained at -110 °C with 0, 4 and 8 equiv. of DMPU. Spectra are shown in Figure S-2.

Figure S-2. DMPU titration of 0.082 M 1a-Li in 19:6 THF/Et2O at -110 °C.

Crypt Titration of 1a-Li. Benzyl phenyl sulfide (15.4 mg, 0.077 mmol) was added to a dried 10 mm NMR tube. The tube was flushed with N2 and 3.0 mL of THF was added. No Et2O was added due to solubility problems withthe crypt solvated lithium reagent. The NMR tube was cooled to !78 °C under positive N2 pressure. The solutionwas metalated with n-BuLi (70 µL, 1.12 M). 13C and 7Li spectra were obtained at -100 °C. Crypt was added as a 1.8M solution in THF and 13C and 7Li spectra were obtained at -100 °C with 0, 0.5, 1 and 2 equiv. of crypt. Spectra areshown in Figure S-3. Note that the 13C anion signals are in rapid equilibrium between the CIP and SIP, since onlyaveraged signals are seen, but the lithium signals are not.

Figure S-3. Crypt[2.1.1] titration of 0.026 M 1a-Li in THF at -100 °C.

S-8

Table S-1. 13C NMR chemical Shifts of 1a-M from Figure 3 in ppm.

Additive C-1 C-2/C-6 C-3/C-5 C-4 C-i C-o C-m C-p

None 156.0 116.3, 119.8 128.6, 127.5 111.5 150.5 124.5 127.9 121.8

DMPU 154.4 111.4, 116.3 129.0, 127.8 103.4 152.4 124.1 128.3 121.3

crypt 154.6 111.7, 116.7 127.9, 127.7 104.5 151.7 124.4 127.8 121.5

HMPA 154.8 111.7, 116.4 128.2, 127.1 103.1 153.7 124.4 127.4 120.7

TAS-F 154.3 111.9, 116.8 127.9, 127.7 104.3 151.4 124.3 127.8 121.7

enolate 154.3 111.7, 116.4 127.9, 127.7 104.5 151.1 124.1 127.9 121.3

HMPA Titration of "-(2-Pyridylthio)benzyllithium (1b-Li). Benzyl 2-pyridyl sulfide (37 mg, 0.18 mmol) wasadded to a dried 10 mm NMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of Et2O wereadded and the NMR tube was cooled to !78 °C under positive N2 pressure. The solution was metalated withn-BuLi (70 µL, 2.5 M). 13C and 7Li spectra were obtained at -115 °C. HMPA was added and 31P and 7Li spectrawere obtained at -115 °C with 1, 2 and 4 equiv. of HMPA (32, 64 and 128 µL) and a 13C spectrum was obtainedwith 4 equiv. HMPA. The sample was quenched with propionic acid (300 µL, 3 M). Spectra are shown in Figure S-4.

Figure S-4. Effect of HMPA on 0.059 M "-(2-Pyridylthio)benzyllithium (1b-Li) in 3:2 THF/Et2O at -115 °C.

180 170 160 150 140 130 120 110 100ppm

3 2 1 0

28 27 26

0

4

7Li 31PEquiv.HMPA

13CHMPA

N

S

Li

155.7

118.3*

114.7

128.6

128.0

110.4

148.4

118.6*

136.8

121.4

176.1N

S 153.7

116.2*

111.1128.4

127.2

103.3

176.9

148.8116.5*

134.4

119.2

1b-Li 1b//Li

H Li(HMPA)4+

S-9

-141 °C

-95 °C

-47 °C

-2 °C

155 150 145 140 135 130 125 120 115 110ppm

Protio

meta

13C NMR Spectra

2635 4

Li

N

N

S

1c-Li

α 2

46

3

5

28 27 26

7Li 31P

0.25

0.5

1.0

4.0

0

equiv.HMPA

S3

C1

S4HMPA

157 154 151 130 125 120 115 110 105ppm

13C

2 0

Li

N

N

S 154.4

115.7

128.4

102.6

127.2

111.7

151.4

126.0

121.2

H

N

N

S 155.9

118.2

128.6

110.2

127.9

115.0

158.0

125.8

122.1

Li(HMPA)4+

1c-Li 1c//Li

α

2

46

1c-Li(HMPA)1

Variable Temperature NMR experiment of "-(N-Methyl-2-imidazolylthio)benzyllithium (1c-Li). Benzyl N-methyl-2-imidazolyl sulfide (95 mg, 0.47 mmol), was added to a dried 10 mm NMR tube. The tube was flushedwith N2 and 1.8 mL of THF and 1.2 mL of ether were added. The NMR tube was cooled to !78 °C under positiveN2 pressure. The solution was metalated with n-BuLi (180 µL, 2.58 M) to give a yellowish green 0.15 M solution oflithium reagent. Internal thermometer (tris(trimethylsilyl)methane,[16g] 2 µL) was added to the solution. 13C spectrawere taken at -140 °C, -95 °C, -47 °C, and -2 °C, where coalescence of the ortho and meta carbon peaks wasobserved. 13C and 7Li spectra were obtained at -140 °C. Spectra are shown in Figure S-5.

Figure S-5. Variable temperature NMR experiment of 0.15 M 1c-Li in 3:2 THF/Et2O.

HMPA Titration of 1c-Li. Benzyl N-methyl-2-imidazolyl sulfide (31 mg, 0.15 mmol) was added to a dried 5mm NMR tube. The tube was flushed with N2 and 360 µL of THF and 240 µL of Et2O were added and the NMRtube was cooled to !78 °C under positive N2 pressure. The solution was metalated with n-BuLi (60 µL, 2.58 M). 13C and 7Li spectra were obtained at -120 °C. HMPA was added and 13C, 31P and 7Li spectra were obtained at -130°C with 0.25 (7 µL), 0.5 (14 µL), 1 (28 µL), 2 (56 µL) and 4 (112 µL) equiv. of HMPA. The sample was quenchedwith cyclohexanone (300 µL, 3 M). Spectra are shown in Figure S-6.

Figure S-6. HMPA titration of 0.23M "-(N-methyl-2-imidazolylthio)benzyllithium (1c-Li) 3:2 in THF/Et2O at -141°C.

S-10

160 155 150 145 140 135 130 125 120 115 110 105 100ppm

2 0

7Li13C

8

4

0

DMPUequiv.DMPU

160 155 150 145 140 135 130 125 120 115 110 105 100 2 00

1

Equiv.Crypt

7Li13C

xx x

DMPU Titration of 1c-Li. Benzyl N-methyl-2-imidazolyl sulfide (41 mg, 0.20 mmol) was added to a dried 10mm NMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of Et2O were added. The NMR tubewas cooled to !78 °C under positive N2 pressure. The solution was metalated with n-BuLi (180 µL, 1.12 M) toafford a pale green solution. 13C and 7Li spectra were obtained at -110 °C. THF (2mL) was added to preventprecipitation. DMPU was added and 13C and 7Li spectra were obtained at -110 °C with 0, 4 and 8 equiv. of DMPU(100 and 200 µL). Spectra are shown in Figure S-7.

Figure S-7. DMPU titration of 0.063 M 1c-Li in 3:2 THF/Et2O at -110 °C.

Crypt solvated 1c-Li. Benzyl N-methyl-2-imidazolyl sulfide (20.4 mg, 0.1 mmol) was added to a dried 10 mmNMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of Et2O were added. The NMR tube wascooled to !78 °C under positive N2 pressure. The solution was metalated with n-BuLi (40 µL, 1.12 M). 13C and 7Lispectra were obtained at -100 °C. Crypt was added as a 1.8M solution in THF and 13C and 7Li spectra were obtainedat -100 °C with 0, 1.1 equiv. of crypt (60 µL). Spectra are shown in Figure S-8.

Figure S-8. Effect of crypt[2.1.1] on 0.033 M 1c-Li in 3:2 THF/Et2O at -110 °C.

S-11

150 140 130 120 110 100 90 80ppm 7.0 6.5 3.5 3.0

-105 °C

-87 °C

-78 °C

-67 °C

-36 °C

-15 °C

5 °C

24 °C

13C 1H

S

Li

Variable Temperature NMR Experiment of 1-(Phenylthio)allyllithium (4a-Li). Allyl phenyl sulfide (45 mg,0.30 mmol) was added to a dried 10 mL RBF. The flask was flushed with N2 and 3.0 mL of THF were added andcooled to !78 °C under positive N2 pressure. The solution was metalated with n-BuLi (270 µL, 1.12 M) to yield ayellow solution. The solution was transferred via cannula to a dried N2 purged 5 mm NMR tube (~800 µL) at !78°C . 13C and 1H spectra were obtained at -105 °C, -87 °C, -78 °C, -67 °C, -36 °C, -15 °C, 5 °C, 24 °C. Spectra areshown in Figures 5 and S-9.

Figure S-9. Variable temperature 13C (left) and 1H (right) NMR experiment of 0.092 M 4a-Li in THF with 0 equiv.of HMPA added.

S-12

0

28 270

0.5

1

1.5

2

3

4

7Li 31PEquiv.HMPA

13CHMPA

160 150 140 130 120 110 100 90 80ppm

S

Li

180 170 160 150 140 130 120 110 100 90 80 70ppm

2 0

28 26

7Li 31P

0

6.0

Equiv.HMPA 13C

N

S

Li

HMPA Titration of 4a-Li. Allyl phenyl sulfide (111 mg, 0.74 mmol) was added to a dried 10 mm NMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of Et2O were added and the NMR tube was cooled to!78 °C under positive N2 pressure. The solution was metalated with n-BuLi (395 µL, 1.90 M) to yield a yellowsolution. 13C and 7Li spectra were obtained at -123 °C. HMPA was added and 13C, 31P and 7Li spectra were obtainedwith 0.5 (64 µL), 1 (128 µL), 1.5 (192 µL), 2 (256 µL), 3 (384 µL) and 4 (512 µL) equiv. of HMPA and the solutionturned from yellow to orange to red. The sample was quenched with methyl iodide (50 µL, 0.80 mmol) to yieldexclusively the alpha methylated product. Spectra and data are shown in Figures 6 and S-10. The assignment ofquaternary and CH carbons was confirmed by a DEPT experiment.

Figure S-10. HMPA titration of 0.22 M 4a-Li in 3:2 THF/Et2O at -123 °C.

HMPA Titration of 1-(2-Pyridylthio)allyllithium (4b-Li). Allyl 2-pyridyl sulfide (66 mg, 0.44 mmol) wasadded to a dried 10 mm NMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of Et2O wereadded and the NMR tube was cooled to !78 °C under positive N2 pressure. The solution was metalated withn-BuLi (390 µL, 1.12 M) to yield a red solution. 13C and 7Li spectra were obtained at -120 °C. HMPA was addedand the solution turned dark red and 31P and 7Li spectra were obtained with 1 and 4 equiv. of HMPA (76 and 306µL) and a 13C spectrum was obtained with 4 equiv. HMPA. Spectra and data are shown in Figures 6 and S-11.

Figure S-11. Treatment of 0.13 M 4b-Li in 3:2 THF/Et2O with HMPA at -120 °C.

S-13

Reactions with Cyclohexenone

In most cases the diastereomers were not separated. In the 1H and 13C spectra below, the major isomer signals,where they could be identified, are marked by an asterisk.

1-("-Phenylthiobenzyl)]-2-cyclohexen-1-ol (2a-H). (45:55 Diastereomer ratio purified by preparative TLC onsilica gel with 20% EtOAc/hexane): 0.35. 1H NMR (300 MHz, CDCl3): * 7.46-7.35 ( m, 2H), 7.29-7.05 ( m, 8H),6.11 (dm, J = 11 Hz), 5.92-5.82* ( m, 1H), 5.65 (dm, J = 10 Hz), 4.23 (s, 1H), 4.18* (s, 1H), 2.28 (broad s, 1H), *2.08-1.45 (m, 6H). 13C NMR (75.4 MHz, CDCl3): * 139.5* (C ), 139.3 ( C), 135.9* (C ), 135.6 ( C), 131.7 (CH),131.5 (CH), 131.2 (CH), 130.9 (CH), 130.3 (CH), 130.0 (CH), 129.6 (CH), 128.6 (CH), 127.8 (CH), 127.2 (CH),127.1 (CH), 126.6 (CH), 126.5 (CH), 72.1 ( C), 71.8* ( C), 65.6 (CH), 65.3* (CH ), 34.2 (CH2), 34.0 (CH2), 25.0(CH2), 25.0 (CH2), 18.6 (CH2), 18.5 (CH2). HRMS (ESI) (m/z): calcd. for C19H20NaOS, [MNa]+ 319.1133; found319.1122.

3-("-Phenylthiobenzyl)cyclohexanone (3a-H). (Diastereomer ratio of 24:76 purified by preparative TLC onsilica gel with 20% EtOAc/hexane): 0.40. 1H NMR (300 MHz, CDCl3): * 7.30-7.10 (m, 10H), * 1.30-1.77 (m, 2H),4.07, 4.04* (d, J = 7 Hz, 1H), 2.76* (dm, J = 13 Hz), 1.78-2.42 (m, 6H). 13C NMR (75.4 MHz, CDCl3): * 210.8 (C), 210.7* ( C), 139.9 (C), 134.8 (CH), 134.7 (C), 132.1 (CH), 132.0 (CH), 128.69 (CH), 128.5 (CH), 128.4 (CH),128.3 (CH), 128.2 (CH), 127.2 (CH), 127.1 (CH), 127.0 (CH), 59.6 (CH), 59.5* (CH), 46.3 (CH2), 45.9 (CH2), 44.2(CH), 44.0* (CH), 41.1 (CH2), 41.1 (CH2), 29.2 (CH2), 28.7 (CH2), 24.7 (CH2). HRMS (EI) (m/z): calcd. forC19H20OS, [M]+ 296.1235; found 296.1249.

1-("-[2-Pyridylthio]benzyl)-2-cyclohexen-1-ol (2b-H). (Single diastereomer purified by preparative TLC onsilica gel with 1:1 hexanes/ether, prep TLC silica gel) 1H NMR (360 MHz, CDCl3), * 8.38 (ddd, J = 5, 2, 1 Hz, 1H),7.46-7.39 (m, 3H), 7.29-7.17 (m, 4H), 6.96, (ddd, J = 7, 5, 1 Hz, 1H), 5.99 (dm, J = 10 Hz, 1H), 5.79 (ddd, J = 10, 5,3 Hz, 1H), 5.08 (s, 1H), 4.01 (bs, 1H), 2.00-1.61 (m, 6H). 13C NMR (90.6 MHz, CDCl3), * 158.4 (C), 148.9 (CH),139.9 (C), 136.2 (CH), 131.3 (CH), 130.6 (CH), 129.5 (CH), 127.9 (CH), 127.2 (CH), 123.0 (CH), 119.8 (CH), 71.8(C), 59.6 (CH), 33.7 (CH2), 25.1 (CH2), 18.6 (CH2). HRMS (ESI) (m/z): calcd. for C18H19NNaOS, [MNa]+

320.1085; found 320.1079.

3-("-[2-Pyridylthio]benzyl)cyclohexanone (3b-H). (Diastereomer ratio of 78:22 purified by preparative TLCon silica gel with 1:1 hexanes/ether, ) 1H NMR (300 MHz, CDCl3), * 8.40 (dd, J = 5, 1 Hz, 1H), 7.44-7.24 (m,6H),7.10, (dd , J = 9, 1 Hz, 1H), 6.94 (ddd, J = 7, 5, 1 Hz, 1H), 5.12, 5.10 (d, J = 7 Hz, 1H), 2.76 (m, 1H), 2.44-1.89(m, 6H), 1.60-1.43 (m, 2H). 13C NMR (75.4 MHz, CDCl3), * 211.0 (CO), 157.9 (C), 149.3 (CH), 40.6 (C), 136.0(CH), 128.4 (CH), 128.3 (CH), 127.2 (CH), 122.8 (CH), 119.7 (CH), 53.2 (CH), 46.0 (CH), 44.6 (CH2), 41.2 (CH2),29.0 (CH2), 24.8 (CH2). HRMS (EI) (m/z): calcd. for C18H19NOS, [M]+ 297.1187; found 297.1197.

1-("-[N-Methyl-2-imidazolylthio]benzyl)-2-cyclohexen-1-ol (2c-H). (Single diastereomer purified on silicacolumn chromatography with 3:1 ethyl acetate/hexanes). 1H NMR (300 MHz, CDCl3), * 7.2-7.21 (m, 5H), 7.09 (d, J= 1 Hz, 1H), 6.87 (d , J = 1 Hz, 1H), 6.42 (dm, J = 10 Hz, 1H), 5.89 (ddd, J = 10, 5, 3 Hz, 1H), 4.74, (bs, OH), 4.23,(s, 1H), 3.12, (s, 3H), 2.11-1.67 (m, 6H). 13C NMR (75.4 MHz, CDCl3), * 140.1 (C), 139.7 (C), 132.1 (CH), 129.7 (CH), 129.3 (CH), 129.0 (CH), 128.1 (CH), 127.3 (CH), 122.7 (CH), 72.5 (CH), 63.4 (CH), 34.5 (CH2), 33.2 (CH3),25.1 (CH2), 18.8 (CH2). HRMS (EI) (m/z): calcd. for C17H20N2OS, [M]+ 301.1374; found 301.1384.

3-("-[N-Methyl-2-imidazolylthio]benzyl)cyclohexanone (3c-H). (Diastereomer ratio of 78:22 purified by silicacolumn chromatography with 3:1 ethyl acetate/hexanes) 1H NMR (300 MHz, CDCl3), * 7.25-7.20 (m, 3H), 7.10-7.07 (m, 3H), 6.80 (d, J = 1 Hz, 1H), 4.25*, 4.19 (d , J = 9 Hz, 1H), 3.17*, 3.10 (s, 3H), 2.98 (m, 1H), 2.64-2.01 (m,4H), 1.97 (m, 1H), 1.83 (m, 1H), 1.57 (m, 1H), 1.35 (m, 1H). 13C NMR (75.4 MHz, CDCl3), * 210.5 (CO), 140.2(C) , 139.1 (C), 129.8, 129.7* (CH), 128.3, 128.3* (CH) , 127.7*, 127.7 (CH), 127.4 (CH), 122.5, 122.5* (CH),60.2, 60.1* (CH), 46.3*, 45.7 (CH2), 42.8*, 42.4 (CH), 41.0 (CH2), 32.9 (CH3), 29.8, 29.0* (CH2), 24.6, 24.5*(CH2). HRMS (EI) (m/z): calcd. for C17H20N2OS [M]+, 300.1296; found 300.1306.

1-(1-[Phenylthio]allyl)cyclohex-2-enol (5a-H). (Diastereomer ratio 50:50 purified by preparative TLC on 1:1hexanes/Et2O) 1H NMR (300 MHz, CDCl3), * 7.46-7.27 (m, 5H), 5.99, 5.97 (dm , J = 10 Hz, 1H), 5.84, 5.75 (dm, J= 10 Hz, 1H), 5.06, 5.04 (ddd, J = 10, 2, 1 Hz, 1H), 4.96, 4.88 (ddd, J = 17, 2, 1 Hz, 1H), 3.65, 3.63 (d, J = 9 Hz,1H), 2.43 (s, 1H), 2.15-1.72 (m, 6H). 13C NMR (75.4 MHz, CDCl3), * 135.5, 135.1 (CH), 135.0 (C), 133.0, 132.1(CH), 132.2, 132.1 (CH), 129.9, 129.6 (CH), 128.8 (CH), 127.3, 127.2 (CH), 117.6, 117.4 (CH2), 65.9, 65.7 (C) ,33.7, 33.4 (CH2), 25.2 (CH2), 18.7, 18.4 (CH2). HRMS (EI) (m/z): calcd. for C15H18OS (M+), 246.1078; found246.1090. The slower moving spot was 1-(3-[Phenylthio]allyl)cyclohex-2-enol (6a-H) as a 55:45 ratio of E/Zisomers.. 1H NMR (300 MHz, CDCl3), * 7.4-7.3 (m, 5H), 6.37, 6.23* (dt, J = 9, 1 Hz; dt, J = 14, 1 Hz, 1H), 6.00*,5.93 (dt, J = 15, 7.5; dt, J = 9, 7.5 1H) , 5.87, 5.83* (dd, J = 4.5, 3, 1H), 5.7-5.6 (m, 1H), 2.52, 2.40* (dt, J = 7.5, 1.5

S-14

Hz; dd, J = 7.5, 1, 2H), 2.1- 1.5 (m).

3-(1-[Phenylthio]allyl)cyclohexanone (7a-H). (Diastereomer ratio of 65:35 purified via preparative TLC on 2:1hexanes/ether, in absence of light) 1H NMR (300 MHz, CDCl3), * 7.40-7.21 (m, 5H), 5.74, 5.69* (ddd, J = 17, 10, 6Hz, 1H), 5.04*, 5.02 (ddd, J = 10, 1.5, 1 Hz, 1H), 4.90, 4.89* (ddd, J = 17, 2, 1 Hz, 1H), 3.50, 3.48* (dd, J = 10, 5.5Hz, 1H), 2.57 (m, 1H), 2.42-2.06 (m, 6H), 1.68-1.52 (m, 2H). 13C NMR (75.4 MHz, CDCl3), * 210.8, 210.7* (CO),136.1, 135.7* (CH), 134.2 (C) , 132.9 (CH), 128.7 (CH), 127.3*, 127.3 (CH), 117.4*, 117.1 (CH2), 58.3, 58.2*(CH), 45.9*, 45.4 (CH2), 42.3 (CH), 41.2*, 41.2 (CH2), 28.8, 27.9* (CH2), 24.8 (CH2). HRMS (EI) (m/z): calcd. forC15H18OS [M]+, 246.1078; found 246.1072. This adduct was observed to undergo a light-induced 1,3 sigmatropicrearrangement of th phenylthio group to afford 3-(3-phenylthio-1-propenyl)-cyclohexanone, characterized by 1HNMR (300 MHz, CDCl3), * 7.36-7.20 (m, 5H), 5.51 (dt, J = 15, 6.5 Hz, 1H), 5.42 (dd, J = 15, 6.5 Hz, 1H), 3.51 (d, J= 6.5 Hz, 2H), 2.38-1.46 (m, 9H). Similar rearrangements were seen by Haynes and coworkers with allyl phenylselenides.[S-11]

1-(1-[2-Pyridylthio]allyl)cyclohex-2-enol (5b-H). (cis*:trans ratio 55:45 purified via preparative TLC with 2:1hexanes/ether, in absence of light) 1H NMR (300 MHz, CDCl3), * 8.48, 8.45 (ddd, J = 5, 2, 1 Hz, 1H), 7.55, 7.53(ddd, J = 8, 7, 2 Hz, 1H), 7.24, 7.21, (dt , J = 8, 1 Hz, 1H), 7.05, 7.03 (ddd, J = 7, 5, 1 Hz, 1H), 6.97(cis) (dt, J = 9, 1Hz, 1H), 6.69 (trans) (dt, J = 15, 1 Hz, 1H), 6.14 (trans) (dt, J = 15, 7.5 Hz, 1H), 6.05 (cis) (dt, J = 10, 7 Hz, 1H),5.86 (ddd , J = 9, 4, 3 Hz, 1H), 5.69, 5.66 (dm, J = 9 Hz, 1H), 2.53 (cis) (ddd, J = 7.5, 2, 1 Hz, 1H), 2.48 (trans) (dt,J = 7, 1 Hz, 1H), 2.15-1.62 (m, 7H). 13C NMR (75.4 MHz, CDCl3), * 158.9, 157.70 (C), 149.5 (CH), 136.4 (CH),132.7, 132.0 (CH), 130.3, 129.8 (CH), 128.2 (CH), 122.3 (CH), 121.9 (CH), 121.7 (CH), 121.5 (CH), 120.1, 119.9(CH), 65.9, 65.4 (C) , 45.9, 42.2 (CH2) 35.6, 35.5 (CH2), 25.2, 25.1 (CH2), 18.9, 18.9 (CH2). HRMS (EI) (m/z):calcd. for C14H17NOS (M+), 247.1031; found 247.1032.

3-(1-[2-Pyridylthio]allyl)cyclohexanone (7b-H). (Diastereomer ratio of 67:33 purified via preparative TLC on2:1 hexanes/ether, in absence of light) 1H NMR (300 MHz, CDCl3), * 8.40 (ddd, J = 5, 2, 1 Hz, 1H), 7.48 (ddd, J =7.5, 7, 2 Hz, 1H), 7.18, (ddd , J = 7.5, 2, 1 Hz, 1H), 6.99 (ddd, J = 7, 5, 1 Hz, 1H), 5.85* (ddd, J = 17, 10, 8.5 Hz,1H), 5.26, 5.24* (ddd, J = 17, 1. 5, 1 Hz, 1H), 5.12*, 5.10 (ddd, J = 10, 2, 1 Hz, 1H), 4.56, 4.51* (dd, J = 8.5, 5 Hz,1H), 2.57 (m, 1H), 2.37-2.06 (m, 6H), 1.68-1.52 (m, 2H). 13C NMR (75.4 MHz, CDCl3), * 211.1, 211.0* (CO),157.7 (C) , 149.4 (CH), 136.1, 136.0* (CH), 135.7 (CH) , 123.5, 123.4* (CH), 119.9 (CH), 117.5*, 117.3 (CH2),52.1 (CH), 45.7*, 45.5 (CH2), 42.8*, 42.7 (CH), 41.3 (CH2), 28.6, 28.3* (CH2), 24.9 (CH2). HRMS (EI) (m/z):calcd. for C15H17NOS [M]+, 247.1031; found 247.1022.

S-15

Table S-1. Reactivity of 1c-Li and 1c-Si in presence of different additives.

Starting material Additive Time Yield 1,2: 1,4 ratio 1,4 dr

1c-Li 0 HMPA 10 min 82 53:29 50:50

1c-Li 4 eq. HMPA 10 min 97 0:100 76:24

1c-Li 4 eq. HMPA 10 min 100 0:100 75:24

1c-Li 8 eq.DMPU 10 min 49 0:100 70:30

1c-Li 4 eq. HMPA 10 min 63 0:100 75:25

1c-Li 1 eq. crypt 10 min 75 0:100 56:44

1c-Si TBAF 10 min 81 0:100 65:35

1c-Li crypt 30 min 102 0:100 52:48

1c-Si TBAF 10 min 57 0:100 65:35

1c-Si TBAF 1 h 26 0:100 61:39

1c-Li 10 eq.HMPA 30 min 100 0:100 76:24

1c-Si TBAF, 6 HMPA 30 min 84 0:100 66:34

1c-Li HMPA 30s 100 0:100 75:25

1c-Li HMPA 5 min 100 0:100 75:25

1c-Li HPMA 30 min 55 0:100 78:22

1c-Si TBAF 10 min 81 0:100 65:35

1c-Li 4 HMPA 30 min 80 0:100 76:24

1c-Si TBAF 30 min 65 0:100 66:34

1c-Si R=Ph TBAF 30 min 76 0:100 66:34

1c-Li crypt 30 min 64 0:100 65:35

1c-Si catalytic cycle 30 min 100 0:100 54:46

S-16

160 150 140 130 120ppm

PhLi, 6 eq. HMPA

Ph3SiF added, -80 °C

Warmed to -30 °C for 30 min

13C

PhLi + 6 eq. HMPA + Ph3SiF PhPh

F

Ph

PhSi

+Li(HMPA)4

Ph4Si

Ph3SiF

TBAT

Ph4Si

PhPh

F

F

PhSi

+Li(HMPA)4

+

TBAT

-115 °C

-80 °C

-80 °C

-80 °C

-80 °C

Reference Spectra

(a)

(b)

(c)

(d)

(e)

(f)

Catalytic Cycle Studies

Reaction of Tributylsilyl Fluoride and n-BuLi in the Presence of HMPA. Tributylsilyl fluoride [S-2] (55 mg,0.25 mmol) and 3 mL of THF were added to a 5 mL long necked RB flask purged with nitrogen. After cooling to -78 °C, HMPA (260 µL, 1.5 mmol) and n-BuLi (100 µL, 2.35 M) was added. The solution was allowed to react at -78 °C for 15 min. A mixture of 2-cyclohexenone and 1a-Si (400 µL, 0.65 M) was added. After stirring for 1 h thesolution was quenched with 200 µL of 3M propionic acid in ether. The solution was taken up in 20 mL of 1:1hexanes/ether, washed with 1x 15 mL NaHCO3, 2 x 15 mL H2O, 1 x 15 mL brine, dried with MgSO4, filtered androtary evaporated. Pentachloroethane (15 µL, 0.125 mmol) was added and the oil was taken up in CDCl3 for 1HNMR. 1a-Si was recovered.

Reaction of Triphenylsilyl fluoride and PhLi in the Presence of HMPA. A 10 mm NMR tube was chargedwith nitrogen and 1.8 mL of THF and 1.2 mL of ether were added. This was cooled to -78 °C and phenyllithium inether (0.34 mmol, 0.15 mL, 2.27 M) was added to the solution to yield a 0.11 M solution. 13C and 7Li spectra wereobtained at -115 °C . HMPA (2.0 mmol, 355 :L) was added and the solution turned light copper in color. 13C, 7Liand 31P spectra were obtained at -115 °C. Recrystallized triphenylsilyl fluoride (96.5 mg, 0.34 mmol) was dissolvedin 200 :L of THF and added to the solution and the solution turned bright copper orange. A small amount ofprecipitate was observed. 13C and 19F spectra were obtained at -80 °C. The solution was warmed to -30 °C for 30min. and 13C and 19F spectra were obtained. The solution turned black with a large amount of white precipitate. Thesolution was quenched with 3M propionic acid and after standard aqueous work-up, crystals were obtained. Spectraare presented in Figure S-12.

Figure S-12. 13C NMR spectra in 3:2 THF/Et2O. (a) A solution fo 0.11 M phenyllithium with 6 equiv. of HMPA. (b) Addition of triphenylsilyl fluoride (TBAT and tetraphenylsilane were observed). (c) After warming to ca. -30 °Cfor 30 min. tetraphenylsilane became the predominate species observed.

S-17

Ph SPh

SiMe3

Ph SPh

H + Li(crypt)

Reference Spectra

1a-Si + TASF

TBAT TBAT TBAT1a-Si + TBAT

(b)

155 150 145 140 135 130 125 120 115 110 105ppm

1a-Si + TBAF(a)

(c)

Ph SPh

H

(d)

(e)

(f)

1a//Li(crypt)

1a-Si

1a-H

-115 °C

-80 °C

-80 °C

Ph SPh

SiMe3

+Ph SPh

H

FSiMe3+-78 °C, THF

M+ F

1a-Si 1a//M

M+

13C

Reaction of 1a-Si with TBAF. 1a-Si (70 mg, 0.25 mmol) was added to a dried 10 mm NMR tube. The tube wasflushed with N2 and 2.5 mL of THF was added. The NMR tube was cooled to !78 °C under positive N2 pressure,and 0.5 mL of Me2O dried with n-BuLi was condensed into the tube. 13C and 29Si spectra of the protio startingmaterial was obtained at 190 K. Tetrabutylammonium fluoride (110 µL, 1.0 M, dried over 4 D MS) was added tothe solution and the solution turned golden yellow. The solution was frozen in N2(R) and allowed to thaw inspectrometer at -115 °C and 13C spectrum was obtained. Only benzyl phenyl sulfide was observed (Figure S-13a).

Figure S-13. 13C NMR spectra. (a) 0.083 M 1a-Si with tetrabutylammonium fluoride in 5:1 THF/Me2O at -115 °C.Only protodesilyaltion (1a-H) was observed. (b) 0.19 M 1a-Si reacting with TASF in THF at -80 °C. A mixture ofsilane 1a-Si and carbanion 1a//TAS are observed. (c) 0.21 M 1a-Si with tetrabutylammoniumdifluorotriphenylsilicate in THF at -80 °C, 18 h at -78 °C and 2 h at 0 °C, spectrum at -80 °C. No carbanion wasobserved, but small amounts of protodesilylation were observed after extended reaction times.

Reaction of 1a-Si with TASF. Tris(dimethylamino)sulfonium difluorotrimethylsiliconate, TASF (36 mg, 0.13mmol) was added to a dried 5 mm NMR tube. The tube was flushed with N2 and 0.5 mL of THF was added. Thewhite solid did not completely dissolve. The NMR tube was cooled to !78 °C under positive N2 pressure, and 13Cand 19F spectra were obtained at -80 °C. 1a-Si (35 mg, 0.13 mmol, in 200 µL THF) was added and the solutionturned golden yellow with precipitate observed and 19F and 13C spectra were obtained. Spectra are shown in FigureS-13b.

Reaction of 1a-Si with TBAT. 1a-Si (28 mg, 0.103 mmol) was added to a dried 5 mm NMR tube. The tube wasflushed with N2 and 300 µL of THF and 200 µL of ether was added. The NMR tube was cooled to !78 °C underpositive N2 pressure,13C spectrum of the silane was obtained at -80 °C. Tetrabutylammoniumdifluorotriphenylsiliconate (TBAT) (53 mg in 500 µL THF) was added to the solution and a 13C spectrum wasobtained immediately at -80 °C and after warming to 0 °C for 2 h, both showed 1a-Si and TBAT and no carbanionsignals. Spectra are shown in Figure S-13c.

S-18

SPh

SiMe3

+ FSPh

HFSiMe3+

+Li(crypt)

-108°C, 5:1 THF:Me2O

+Li(crypt)Ph Ph

155 150 141 138 130 125 120 115 110 105ppm

0 -2

SPh

H+Li(crypt)

FSiMe3

SPh

SiMe3

FSiMe3 added

13C

Ph

Ph

SPh

H

Ph

1//Li(crypt) 1a-Si

X

Reference Spectra

(a)

(b)

(c)

(d)

(e)

Reaction of Crypt-Solvated "-(Phenylthio)benzyllithium with Trimethylsilyl Fluoride. Benzyl phenylsulfide (22 mg, 0.11 mmol) was added to a dried 10 mm NMR tube. The tube was flushed with N2 and 2.5 mL ofTHF was added. The NMR tube was cooled to !78 °C under positive N2 pressure, and 0.5 mL of Me2O dried withn-BuLi was condensed into the tube. The solution was metalated with n-BuLi (40 µL, 2.7 M). 13C and 7Li spectrawere obtained at -115 °C. Crypt[2.1.1] (30 µL, 0.11 mmol) was added, the solution turned bright gold and 13C and7Li spectra were taken. Trimethylsilyl fluoride (1.5 mL of gas) was condensed into the NMR tube and 13C and 7Lispectra were taken at -115 °C. Spectra are shown in Figure S-14.

Figure S-14. (a) 13C NMR spectrum of 0.19 M 1a//Li(crypt) in 5:1THF/Me2O at -115 °C. (b) Addition oftrimethylsilyl fluoride. No 1a-Si was formed, but minor amounts of 1a-H are observed. (c)-(e) Reference 13C NMRspectra of 1a-H, 1a-Si and FSiMe3.

S-19

156 154 3 1 -1 -3142 140 138 130 125 120 115 110 105ppm

Ph SPh

SiMe3

90 min at -80 °C

120 min at -40 °C

Ph SPh

H

Ph SPh

SiMe3

+Ph SPh

H

Ph SPh

SiMe3

++Li(HMPA)4 +Li(HMPA)4

1a-Si added

1a-Si1a// Li(HMPA)4Reference Spectrum

1a//Li(HMPA)4

+Li(HMPA)4

(a)

(b)

(c)

(e)

(d)

13C

Check for Proton Transfer of 1a-Si. Benzyl phenyl sulfide (58 mg, 0.29 mmol) was added to a dried 10 mmNMR tube. The tube was flushed with N2 and 1.8 mL of THF and 1.2 mL of ether were added. The NMR tube wascooled to !78 °C under positive N2 pressure. The solution was metalated with n-BuLi (105 µL, 2.5 M) and HMPA(200 µL, 1.15 mmol) was added. A 13C spectrum was obtained. Silane 1a-Si (68 mg, 0.25 mmol) was added in 200µL THF. A 13C spectrum was obtained after 90 min at -80 °C, the solution was warmed to -50 °C for 3 h and a 13Cspectrum was obtained. Spectra are shown in Figure S-15.

Figure S-15. (a) 13C NMR spectra of 0.085 M HMPA-solvated 1a//Li in 3:2 THF/Et2O at -80 °C. (b) Addition of 1a-Si and immediate acquisition of 13C spectrum. (c) After 90 min at -80 °C. (d) after 120 min. at -50 °C.

S-20

Reaction of Crypt-Solvated Lithium Enolate of Cyclohexanone with TMSF. 1-(Trimethylsiloxy)cyclohexene(90 mg, 0.40 mmol) was added to a dried 10 mm NMR tube, purged with nitrogen, 3 mL of THF were added, thesample was cooled to -78 °C and cleaved with n-BuLi (140µL, 2.83 M). The solution was warmed to -15 °C for 45min. to allow for trimethylsilyl cleavage, and cooled back down to -80 °C and 13C and 7Li spectra were taken. Thesample was diluted by removing 2.25 mL of sample and replacing with 2 mL of THF. Crypt[2.1.1] (30 µL, 0.11mmol) was added and 13C and 7Li spectra were taken at -80 °C. Trimethylsilyl fluoride (2 mL of gas) was condensedin the NMR tube and 13C and 7Li spectra were taken at -80 °C. Spectra are shown in Figure S-16.

Figure S-16. (a) 13C NMR spectra of 0.036 M lithium enolate of cyclohexanone. (b) Addition of 1.0 equiv of cryptenolate. (c) Addition of trimethylsilyl fluoride in THF at -80 °C to form the enol silyl ether. (d) Reference spectrumof enol silyl ether.

160 155 150 100 95 90 85ppm 0 -2

OLi

crypt[2.1.1]

O//+Li(crypt) FSiMe3

OSiMe3

+F

THF -80°C

OLi(crypt)

crypt[2.1.1] added

FSiMe3 added

OSiMe3

//+Li(crypt)

FSiMe3

13C

x

OLi(a)

(b)

(c)

(d)

Reference Spectrum

S-21

160 0

1a//Li(crypt) 5:1 THF:Me2O

+ +

1a-Si 1a//Li(crypt)

+Li(crypt)

1.8 Eq. crypt added

138 130 125 120 115 110 105ppm

90 85153

13C

1a-Si added

H

Ph SPh

SiMe3

Ph SPh

H3:2 THF:Et2O,-120 °C

Reference Spectra Ph SPh

(a)

(b)

(c)

(d)

(e)

(f)

OLi(crypt)

OSiMe3

OLi

OLi(crypt) OSiMe3

Reaction of Crypt Solvated Lithium Enolate of Cyclohexanone with 1a-Si. A dried 10 mm NMR tube wasflushed with N2 and 1.8 mL of THF and 1.2 mL of ether were added. The NMR tube was cooled to !78 °C underpositive N2 pressure and n-BuLi (60 µL, 2.5 M) and diisopropylamine (22 µL, 0.16 mmol) were added. The solutionwas warmed to 0 °C in an ice bath for 30 min and cooled back down to -78 °C. Cyclohexanone (150 µL, 1.0 Msolution in THF) was added allowed to react 30 min. 13C and 7Li spectra were acquired at -80 °C. Crypt (150 µL,1.8 M solution in THF) was added and 13C and 7Li were taken at -110 °C. 1a-Si (36 mg, 0.13 mmol) was added in500 µL of THF. The solution turned bright yellow. A 13C spectrum was obtained at -110 °C. The solution wasstored overnight at !78 °C and 13C and 7Li spectra were acquired at -110 °C. The solution was stored overnight at!78 °C and quenched with trimethylsilyl chloride (30 µL) and 13C and 7Li spectra were acquired at -110 °C. Spectra are shown in Figure S-17.

Figure S-17. (a) 13C spectrum of 0.047 M lithium enolate of cyclohexanone. (b) Addition of 1.8 equiv ofcrypt[2.1.1]. (c) Addition of silane 1a-Si in 3:2 THF/Et2O at -110 °C to form the carbanion 1//Li(crypt) and the enolsilyl ether. Minor amounts of protonation were also observed. (d)-(f) 13C NMR spectra of phenyl benzyl sulfide, 1-(trimethylsiloxy)cyclohexene, and 1a//Li(crypt) are shown for comparison.

S-22

100 90ppm

0 -5

OLi

OLi(HMPA)

SiMe3

PhS Ph

OSiMe3

6 equiv. HMPA

160 150 140 130

OLi(HMPA)

+

OSiMe3

+

1a-Si 3:2 THF:Et2O;-78 °C

add 1a-Si

Reference Spectra

add Me3SiCl

(a)

(b)

(c)

(d)

(e)

(f)

Ph SPh

SiMe3

Ph SPh

H +Li(HMPA)4

13C

Reaction of HMPA Solvated Lithium Enolate with Silane 1a-Si. A dried 10 mm NMR tube was flushed withN2 and 1.8 mL of THF and 1.2 mL of ether were added. The NMR tube was cooled to !78 °C under positive N2pressure and n-BuLi (120 µL, 2.5 M) and diisopropylamine (42 µL, 0.30 mmol) were added to the solution. Thesolution was warmed to 0 °C in an ice bath for 30 min and a 7Li spectrum was obtained at -115 °C to check forcomplete reaction of n-BuLi. Cyclohexanone (300 µL, 1.0 M solution in THF) was added and 13C and 7Li spectrawere acquired at -115 °C. HMPA (312 µL, 1.8 mmol) was added and 13C, 7Li, 31P spectra were obtained at -120°C. 1a-Si (68 mg, 0.25 mmol) was added in 300 µL of THF. A 13C NMR spectrum was obtained at -80 °C. Thesolution was stored at !78 °C for 16 h and 13C and 7Li spectra were obtained at -80 °C and -105 °C. The solutionwas quenched with trimethylsilyl chloride (40 µL, 0.31 mmol) and a 13C NMR spectrum was obtained at -105 °C. Spectra are shown in Figure S-18.

Figure S-18. (a) 13C NMR spectrum of 0.089 M lithium enolate of cyclohexanone in 3:2 THF/Et2O at -120 °C. (c)addition of 6 equiv. of HMPA. (d) Addition fo 1a-Si. No carbanion 1a//Li(HMPA) or enol silyl ether wereobserved. Upon addition of trimethylsilyl chloride, 1-(trimethylsiloxy)cyclohexene was observed. (e)-(f) 13C NMRspectra 1a-Si and 1-trimethylsiloxycyclohexene are shown for comparison.

Catalytic cycle with HMPA. Benzyl phenyl sulfide (15 mg, 0.075 mmol) was added to a 25 mL RBF flask andthe flask was purged with nitrogen, and to this was added 8 mL THF and cooled to -78 °C. This was metalated withn-BuLi (30 µL, 2.58 M, 0.077 mmol), the solution turned yellow and HMPA (52 µL, 0.30 mmol) was added. Uponaddition of HMPA, the solution turned orange. 1a-Si (204 mg, 0.75 mmol) and 2-cyclohexenone (73 µL, 0.75 mmol)were added to the solution and allowed to react 30 min at -78 °C. The solution was quenched with propionic acid(600 µL, 3 M), taken up in 60 mL 1:1 hexanes/ether, washed 1x 40 mL NaHCO3, 1 x 40 mL H2O, 1 x 40 mL brine,dried MgSO4, rotary evaporated, pentachloroethane (9 µL, 0.075 mmol) was added as an internal standard andproduct ratios were determined by 1H NMR spectroscopy.

S-23

References

[S-1] Watson, S. C.; Eastham, J. F. J. Organomet. Chem. 1967, 9, 165-168.[S-2] Voronkov M. G.; Skorik, Y. I. lzv. Akad. Nauk SSSR, Ser. Khim. 1964, 7, 1215-1221. Eaborn, C. J. Chem.

Soc., Abstracts 1952, 2846-9.[S-3] Iranpoor, N.; Firouzabadi, H.; Shaterian, H. R. J. Org. Chem. 2002, 67, 2826 - 2830.[S-4] Piffl, N.; Weston, J.; Guenter, W.; Anders, E. J. Org. Chem. 2000, 65, 5942-5950.[S-5] Goux, C; Lhoste, P.; Sinou, D. Tetrahedron 1994, 50, 10321-10330.[S-6] Pilcher, A. S.; Ammon, H. L.; DeShong, P. J. Am. Chem. Soc. 1995, 117, 5166-5167. Pilcher, A. S.;

DeShong, P. J. Org. Chem. 1999, 61, 6901-6905.[S-7] Danheiser, R. L.; Fink, D. M. Tetrahedron Lett. 1985, 26, 2509-2512.[S-8] Dziadulewicz, E.; Hodgson, D.; Gallagher, T. J. Chem. Soc., Perkins Trans. 1 1988, 3367-3379.[S-9] Hiroi, K.; Sato, H.; Chen, L.-M.; Kotsuji, K. Chem. Pharm. Bull. 1987, 35, 1413-1426.

[S-10] Bacci, J. P.; Greenman, K. L.; Van Vranken, D. L. J. Org. Chem. 2003, 68, 4955 - 4958.[S-11] Binns, M. R.; Haynes, R. K. J. Org. Chem. 1981, 46, 3790-3795.

9 8 7 6 5 4 3 2 1 0ppm

1.00 0.930.96

3.012.862.05

8.50 8.45 8.407.00 6.957.15 7.10

4.43

6.94

6.94

6.95

6.96

6.96

6.96

6.98

6.98

7.12

7.15

7.25

7.28

7.38

7.39

7.39

7.41

8.43

8.43

8.44

8.44

8.45

8.45

8.45

8.45

(1H, CDCl3, 300 MHz)

N

S

1b-H

240 220 200 180 160 140 120 100 80 60 40 20 0ppm

34.3

119.

512

2.0

127.

012

8.4

128.

9

135.

913

7.9

149.

3

158.

7

(13C, CDCl3, 300 MHz)

S-24

9 8 7 6 5 4 3 2 1 0ppm

2.18

3.00

2.58

2.53

1.00

6.85 6.80

7.30 7.25 7.20 7.15 7.10 7.05 7.00

3.22

4.14

6.85

6.85

7.10

7.11

7.22

7.22

7.23

7.24

7.24


N

N S

1c-H

200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0ppm

33.0

40.0

122.

3

127.

312

8.4

128.

712

9.6

137.

814

0.4

(13C, CDCl3, 90.6 MHz)

S-25

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

9.02

9.74

0.10

3.75


S

Si

1a-Si

S-26

240 220 200 180 160 140 120 100 80 60 40 20 0ppm

-2.6

41.0

125.

212

5.4

127.

512

7.8

128.

212

8.5

138.

214

1.1

(13C, CDCl3, 75.4 MHz)

1a-Si

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

7.65

2.942.48

9.37

0.20

0.38

1.23

4.08

S

Si

1a-Si (R = iPr)

220 200 180 160 140 120 100 80 60 40 20 0ppm

-6.6

12.3

17.6

17.6

39.0

125.

312

5.4

127.

812

8.0

128.

212

8.5

138.

214

1.3

(13C, CDCl3, 300 MHz)

S-27


10 9 8 7 6 5 4 3 2 1 0ppm

1.00

7.13

15.98

0.34

0.41

3.91

7.08

7.11

7.11

7.15

7.16

7.32

7.34

7.34

7.36

7.43

7.43

7.45

S

Si

1a-Si (R = Ph)


220 200 180 160 140 120 100 80 60 40 20 0ppm

-4.4

-4.0

40.7

125.

312

5.5

127.

612

7.8

127.

912

8.0

128.

512

9.5

133.

013

4.3

135.

713

8.0

140.

5

(13C, CDCl3, 75.4 MHz)

S-28

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

8.99

0.930.90

0.70

2.02

2.89

0.85

8.368.348.32

4.30 4.25

7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80

0.10

4.29

6.85

6.86

6.86

6.87

6.87

6.88

6.89

7.03

7.06

7.09

7.11

7.20

7.22

7.25

7.26

7.33

7.34

7.34

7.36

8.33

8.33

8.34

8.35


N

S

SiMe3

1b-Si

240 220 200 180 160 140 120 100 80 60 40 20 0ppm

-2.6

37.2

119.

312

1.6

125.

412

7.7

128.

0

135.

9

141.

5

149.

3

160.

1(13C, CDCl3,75.4 MHz)

S-29

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

3.14

9.08

0.920.90

4.89

7.006.98 6.766.74

0.13

3.33

3.98

6.74

6.75

6.99

7.00

7.08

7.08

7.09

7.12

7.12

7.17

7.19

7.19


N

N S

SiMe3

1c-Si

220 200 180 160 140 120 100 80 60 40 20 0ppm

-2.5

33.1

43.4

76.6

77.0

77.4

122.

1

125.

712

7.9

128.

012

9.5

141.

714

1.9

(13C, CDCl3, 75.4 MHz)

S-30

9 8 7 6 5 4 3 2 1 0ppm

1.00

0.550.45 0.46

0.55

0.92

6.43

1.90

7.71

6.20 6.15 6.10

5.95 5.90 5.85

5.70 5.65

4.30 4.25 4.20

2.35 2.30 2.25 2.20

2.25

2.32

4.22

4.26

5.67

5.70

5.91

5.92

5.93

6.13

6.13

6.13

6.16

6.16

6.17


2a-H

HO

SPh

Ph

220 200 180 160 140 120 100 80 60 40 20 0ppm

18.5

18.6

25.0

25.0

34.0

34.2

65.3

65.6

71.8

72.1

126.

512

6.6

127.

112

7.2

127.

812

8.6

129.

613

0.0

130.

313

0.9

131.

213

1.5

131.

713

5.6

135.

913

9.3

139.

5

(13C, CDCl3, 75.4 MHz)

S-31

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

2.24

4.30

0.99 1.03

1.00

1.080.86 0.96

5.44

6.958.408.388.36

7.45 7.40 7.35 7.30 7.25 7.20 7.15

6.00 5.95 5.90 5.85 5.80 5.75

1.61

1.61

1.62

1.62

1.71

1.74

1.75

1.99

2.00

4.01

5.08

5.77

5.78

5.79

5.79

5.80

5.81

5.81

5.98

6.00

6.96

6.96

6.97

6.97

6.98

6.98

6.98

7.19

7.25

7.26

7.27

7.44

7.46

8.37

8.37

8.39

8.39

HO

Ph

N

S

220 200 180 160 140 120 100 80 60 40 20 0ppm

18.6

25.1

33.7

59.6

71.8

119.

812

3.0

127.

212

7.9

129.

513

0.6

131.

313

6.2

139.

9

148.

9

158.

5(13C, CDCl3, 90.6 MHz)


S-32

2b-H

HOPh

9 8 7 6 5 4 3 2 1 0ppm

0.690.70

3.93

0.98 1.000.98

0.64

2.83 2.11

4.36

6.40 6.35

5.90 5.85 5.80

6.806.786.766.74

3.65 3.60 3.55

7.05 7.00

1.37

1.37

1.37

1.38

1.38

1.38

1.38

1.39

1.39

1.39

1.40

1.40

1.40

1.62

1.62

1.64

1.64

1.99

1.99

2.00

2.00

2.00

2.00

2.00

2.01

2.01

3.09

3.59

4.20

5.82

5.82

5.82

5.82

5.84

5.85

5.85

5.86

6.33

6.33

6.34

6.34

6.37

6.37

6.78

6.78

7.05

7.06

7.17

7.24


2c-H

N

S N

(13C, CDCl3, 90.6 MHz)

S-33

160 140 120 100 80 60 40 20 0ppm

18.8

25.1

33.2

34.6

63.5

72.5

122.

6

127.

312

8.0

129.

012

9.3

129.

613

2.1

139.

714

0.1

SPh

O

Ph

9 8 7 6 5 4 3 2 1 0ppm

4.10 4.05 2.80 2.75

2.74

2.75

2.78

2.79

2.79

4.04

4.06

4.09

7.15

7.22

7.23

(13C, CDCl3, 75.4 MHz)

3a-H

220 200 180 160 140 120 100 80 60 40 20 0ppm

24.7

28.7

29.2

41.1

44.0

44.2

45.9

46.3

59.5

59.6

127.

012

7.1

127.

312

7.9

128.

212

8.3

128.

412

8.5

128.

712

9.6

132.

013

2.1

134.

713

4.8

139.

9

210.

721

0.8

(13C, CDCl3, 75.4 MHz)

S-34

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

1.12

1.17

7.19

1.22

0.93

3.43

2.29

1.56 1.97

5.15 5.10 2.80 2.75 2.70 2.05 2.00 1.95 1.90 1.85

7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90

1.50

1.88

1.88

1.88

1.92

1.92

1.93

2.00

2.05

2.19

2.19

2.20

2.24

2.24

2.36

2.72

2.73

2.73

2.73

2.77

2.77

2.78

5.08

5.10

6.92

6.93

6.94

6.94

6.96

7.08

7.11

7.11

7.30

7.34

7.34

8.38

8.38

8.39

8.39

8.40


N

S

O

Ph

240 220 200 180 160 140 120 100 80 60 40 20 0ppm

24.8

29.0

41.2

44.6

46.0

46.1

53.2

53.3

53.4

119.

712

2.8

122.

912

7.2

128.

312

8.4

128.

413

6.0

140.

514

0.6

149.

3

157.

9

211.

0

(13C, CDCl3, 75.4 MHz)

S-35

3b-H

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

2.94

0.79

4.83

3.18

0.83

0.91

2.98

2.90

4.25 4.203.00 2.95 2.90

3.15 3.10

7.25 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75

1.28

1.29

1.29

1.30

1.33

1.33

1.33

1.34

1.54

1.57

1.59

1.79

1.93

1.98

2.25

2.29

2.33

2.34

2.43

2.46

2.93

2.94

2.94

2.98

3.08

3.15

4.17

4.20

4.23

4.26

6.78

6.79

6.98

6.99

7.00

7.05

7.06

7.21

7.22


O

S N

NPh

3c-H

240 220 200 180 160 140 120 100 80 60 40 20 0ppm

24.5

29.0

29.8

33.0

41.1

42.4

42.8

45.7

46.3

60.1

60.2

122.

512

2.5

127.

412

7.7

127.

712

8.3

128.

312

9.7

129.

813

9.1

139.

714

0.2

210.

5

(13C, CDCl3, 75.4 MHz)

(13C, CDCl3, 90.4 MHz, DEPT 135)

S-36

9 8 7 6 5 4 3 2 1 0

5.55

1.00

2.142.10

5.15 5.10 5.05ppm

5.90 5.85 5.80ppm

3.55 3.50ppm

3.52

3.54

5.03

5.04

5.07

5.07

5.09

5.09

5.14

5.15

5.82

5.85

5.88

5.91

7.14

7.26

7.28

7.31

7.32

7.34

7.34

S

4a-H


220 200 180 160 140 120 100 80 60 40 20 0ppm

37.1

117.

5

126.

112

8.7

129.

713

3.5

135.

9

(13C, CDCl3, 75.4 MHz)

S-37

10 9 8 7 6 5 4 3 2 1 0

1.00 0.991.07

2.19

0.99

1.080.92 1.07

6.05 6.00 5.95 5.90ppm

8.448.428.40ppm

7.55 7.50 7.45 7.40 7.35 7.30 7.25 7.20 7.15 7.10 7.05 7.00 6.95ppm

5.35 5.30 5.25 5.20 5.15 5.10 5.05ppm

3.85 3.80ppm

3.83

3.85

5.09

5.12

5.12

5.26

5.26

5.31

5.32

6.95

6.96

6.97

6.97

6.98

6.99

6.99

7.15

7.15

7.16

7.16

7.17

7.18

7.18

7.19

7.44

7.44

7.46

7.47

7.47

7.47

7.49

7.50

8.42

8.42

8.43


N

S

4b-H

240 220 200 180 160 140 120 100 80 60 40 20 0ppm

33.0

117.

411

9.4

122.

2

133.

813

5.8

149.

4

158.

5

(13C, CDCl3, 75.4 MHz)

S-38

9 8 7 6 5 4 3 2 1 0ppm

2.15

0.96 1.00

9.23

5.87

5.85 5.80 5.75 5.705.05 5.00 4.95

3.25

0.17

3.24

3.27

4.93

4.93

4.93

4.96

4.96

4.97

4.99

5.04

5.05

5.70

5.73

5.74

5.79

7.24

7.29

S

SiMe3

4a-Si


240 220 200 180 160 140 120 100 80 60 40 20 0ppm

-2.9

39.3

76.6

77.0

77.4

114.

1

125.

512

8.5

128.

8

136.

913

7.4

(13C, CDCl3, 75.4 MHz)

S-39

9 8 7 6 5 4 3 2 1 0ppm

1.00 1.101.09

1.08

1.360.95

1.151.06

9.88

5.90 5.85 5.80 5.753.75 3.70

5.15 5.10 5.05 5.00 4.95 4.90

0.13

0.13

3.70

3.73

4.93

4.96

5.11

5.16

5.77

5.79

5.80

5.83

6.91

6.91

6.91

6.93

6.93

6.93

6.95

7.15

7.18

7.42

7.42

7.42

7.44

7.45

8.37

8.39

8.39


N

S

SiMe3

4b-Si

240 220 200 180 160 140 120 100 80 60 40 20 0 -20ppm

-2.9

35.7

76.6

77.0

77.4

114.

0

119.

412

2.1

135.

913

6.6

149.

3

159.

9

(13C, CDCl3, 75.4 MHz)

S-40

10 9 8 7 6 5 4 3 2 1 0ppm

1.000.942.112.98

5.23 6.65

3.65 3.60

5.05 5.00 4.95 4.90 4.85

6.00 5.95 5.90 5.85 5.80 5.75 5.70

1.78

1.79

1.83

1.85

2.06

2.07

2.07

2.07

2.07

2.12

2.12

2.13

2.13

2.13

2.40

3.59

3.62

3.64

4.89

4.90

4.90

4.92

4.92

4.92

5.04

5.04

5.06

5.75

5.77

5.80

5.82

5.83

5.93

5.95

5.95

5.96

5.96

7.26

7.26

7.26

7.28

7.41

7.41

HO

S

5a-H


220 200 180 160 140 120 100 80 60 40 20 0ppm

1.0

18.4

18.7

25.2

33.4

33.8

65.7

65.9

76.6

77.0

77.4

117.

411

7.6

127.

212

7.3

128.

812

9.6

129.

913

2.1

132.

213

2.6

133.

013

5.0

135.

113

5.5

(13C, CDCl3, 90.6 MHz)

(13C, CDCl3, 90.6 MHz, 135 DEPT)

S-41

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

13.26

2.61

1.06

2.18

2.60 2.55 2.50 2.45 2.40 2.35ppm

6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6ppm

5.82

15.

831

5.83

55.

845

5.85

55.

864

5.86

95.

879

5.92

15.

927

5.94

75.

949

5.95

35.

974

5.97

65.

978

5.99

96.

024

6.04

9

6.21

36.

217

6.22

0

6.26

36.

266

6.27

0

6.35

36.

357

6.36

16.

384

6.38

8

S-42

x

x

x


HO

S

6a-H

10 9 8 7 6 5 4 3 2 1 0ppm

1.00

1.090.98

1.08

0.50

0.43 1.06

1.00

1.00 2.08

8.72

2.55 2.50 2.45

8.50 8.45 8.40

7.55 7.50 7.456.70 6.657.10 7.05 7.00 6.95

6.20 6.15 6.10 6.05 6.00 5.95 5.90 5.85 5.80 5.75 5.70 5.65 5.60

1.62

1.62

1.62

1.62

1.69

1.73

2.03

2.03

2.03

2.04

2.04

2.04

2.09

2.09

2.10

2.10

2.46

2.49

5.66

5.83

5.83

6.02

6.05

6.13

6.16

6.64

6.69

6.94

6.98

7.01

7.04

7.04

7.20

7.21

7.24

7.52

8.45

8.45


240 220 200 180 160 140 120 100 80 60 40 20 0ppm

18.9

18.9

25.1

35.5

35.6

42.2

45.9

69.5

70.0

76.6

77.0

77.4

119.

912

0.1

121.

512

1.7

121.

912

2.3

128.

213

0.3

130.

413

1.9

132.

013

2.7

136.

414

9.5

149.

6

157.

715

8.9

(13C, CDCl3, 300 MHz)

S-43

HO

S

6b-H

N

9 8 7 6 5 4 3 2 1 0ppm

1.000.84 1.22

0.92

4.77

0.99

6.13

2.06

3.50 3.45

5.75 5.70 5.65

2.60 2.55 2.505.05 5.00 4.95 4.90 4.85 4.80

1.54

1.58

2.05

2.05

2.06

2.08

2.08

2.08

2.08

2.09

2.10

2.28

2.30

2.34

2.35

2.35

2.36

3.46

3.48

4.85

4.85

4.85

4.91

4.91

4.91

5.01

5.04

5.04

5.69

5.72

7.25

7.27

7.36

7.36


O

S

7a-H

220 200 180 160 140 120 100 80 60 40 20 0ppm

1.4

24.8

28.0

28.8

41.2

41.2

42.4

45.4

45.9

58.2

58.3

117.

111

7.3

127.

312

7.3

128.

612

8.7

128.

912

9.0

129.

613

2.9

132.

913

5.8

136.

2

210.

621

0.7

(13C, CDCl3, 90.6 MHz)

(13C, CDCl3, DEPT 135, 90.6 MHz)

S-44

9 8 7 6 5 4 3 2 1 0ppm

1.001.08

1.03

0.97

1.16 1.050.99 1.03

1.16

7.02

2.39

5.90 5.85 5.80 4.60 4.55 4.50

5.30 5.25 5.20 5.15 5.10

8.45 8.40 7.50 7.45

7.20 7.15

7.00 6.95

1.60

2.09

2.09

2.10

2.23

2.24

2.24

2.27

2.27

2.36

2.57

4.52

4.53

4.54

4.54

4.54

5.10

5.10

5.10

5.13

5.13

5.14

5.14

5.22

5.22

5.27

5.27

5.27

5.28

5.81

5.82

5.85

5.87

6.99

6.99

7.01

7.16

7.19

7.45

7.47

7.47

7.48

7.48

8.41

8.41

8.42

8.43


220 200 180 160 140 120 100 80 60 40 20 0ppm

24.9

24.9

28.3

28.6

41.3

42.7

42.8

45.5

45.7

52.1

76.6

77.0

77.3

117.

211

7.5

119.

912

3.4

123.

5

135.

613

6.0

136.

1

149.

4

211.

021

1.1

(13C, CDCl3, 90.6 MHz)

(13C, CDCl3, 90.6 MHz, 135 DEPT)

S-45

O

S

7b-H

N

9 8 7 6 5 4 3 2 1 0ppm

1.90

1.70

1.000.75

2.97

9.53

3.25 3.20 1.841.821.80

0.25

1.82

1.83

3.23

3.23

3.24

3.25

7.19

7.28

7.28

7.29

7.31

7.31

7.34

7.46

7.46

7.46

7.48

7.48

7.49


220 200 180 160 140 120 100 80 60 40 20 0ppm

-2.93.8

25.0

77.5

78.3

125.

712

8.5

128.

6

137.

6

(13C, CDCl3, 75.4 MHz)

S-46

PhS

SiMe3

9-Si

studies on the reactive species in fluoride-mediated ... supporting information studies on the...

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