Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007

S1

Efficient and General One-Pot Synthesis of Diaryliodonium Triflates: Optimization, Scope and Limitations

Marcin Bielawski, Mingzhao Zhu and Berit Olofsson*

Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden.

berit@organ.su.se

SUPPORTING INFORMATION

1. Optimization studies S2-S3

2. Reaction conditions for synthesis of salts 3 S4-S5

3. Analytical data of diaryliodonium salts 3 S6-S13

3. Limitations to the developed protocol S13-S14

4. References S14

5. NMR spectra of diaryliodonium salts 3 S15-S70

S2

1 Optimization studies

1.1 The use of mCPBA and TfOH to synthesize 3a. Stoichiometric amounts of all components resulted in a sluggish reaction (Table S1, entry 1). No iodobenzene could be recovered, which is indicative of a working oxidation process but inefficient EAS. In order to increase the reaction rate of the EAS step, 2 equiv TfOH was employed, which indeed resulted in a much faster formation of 3a (entries 2, 3). An increase of mCPBA to 2 equivalents instead resulted in decreased yield (entry 4), which could be due to over-oxidation to iodine(V). The amount of benzene (2a) also had an impact on the reaction outcome, as depicted in entries 5, 6. Increasing the temperature considerably reduced the reaction time, delivering 3a in good yields after 3 h at 40 °C (entry 7) or 10 min at 80 °C (entry 8). Pleasingly, the use of 3 equiv. of TfOH delivered 3a in 89% yield (entry 9). A subsequent temperature study with the optimized conditions revealed that the reaction is much faster than we had anticipated (Table S2). Thus, the reaction was complete within 10 min at temperatures down to -50 ºC, and 0 ºC or rt was deemed to be the most convenient temperature for further reactions. Control experiments with 2 equiv. TfOH showed that the reactivity is considerably decreased with less acid (Table S1, entries 10, 11). Changing the solvent to Et2O, CHCl3 or CH3CN resulted in decreased yields (entries 12-14), whereas changes in concentration were less important (entries 15-17). We subsequently investigated whether TfOH was needed in the oxidation or only mediated the EAS step. Thus, iodobenzene, mCPBA and benzene were reacted in the absence of TfOH, which indeed gave a slow oxidation but no salt formation (entry 18). Purification by flash chromatography in CH2Cl2/MeOH instead of precipitation gave 3a in slightly reduced yield (entry 19). Table S1: Optimization of reaction conditions for synthesis of salt 3a.[a]

I

mCPBA,

I OTf

1a 2a 3a

TfOH, CH2Cl2

Entry 2a

(equiv.) mCPBA (equiv.)

TfOH (equiv.)

T (ºC) Time Yield (%)[b]

1 1.1 1.1 1.1 rt 18 h 5 2 1.1 1.1 1.5 rt 2.5 h 61 3 1.1 1.1 2 rt 18 h 68 4 1.1 2 2 rt 18 h 60 5 2 1.1 2 rt 18 h 75 6 5 1.1 2 rt 21 h 82 7 1.1 1.1 2 40 3 h 83 8 1.1 1.1 2 80 10 min 73 9 1.1 1.1 3 80 10 min 89

10 1.1 1.1 2 rt 10 min 58 11 1.1 1.1 2 0 10 min 56

12[c] 1.1 1.1 3 0 10 min 5 13[d] 1.1 1.1 3 0 10 min 66 14[e] 1.1 1.1 3 0 10 min -[i] 15[f] 1.1 1.1 3 0 10 min 84 16[g] 1.1 1.1 3 0 10 min 91 17[h] 1.1 1.1 3 0 10 min 52 18 1.1 1.1 0 0 10 min -[j]

19 1.1 1.1 3 0 10 min 79[k] [a] Reaction conditions: 1a (1.0 equiv., 0.23 mmol), 2a and mCPBA were dissolved in CH2Cl2 (1 mL), TfOH was added dropwise at 0 ºC (or tabulated temp. if lower) and the reaction was stirred at the indicated temperature and

S3

time. [b] Isolated yield. [c] In Et2O. [d] In CHCl3. [e] In CH3CN. [f] In CH2Cl2 (2 mL). [g] In CH2Cl2 (0.5 mL). [h] No

solvent was used. [i] No precipitation. [j] To see if the oxidation took place, see text. [k] Isolated by flash chromatography.

Table S2: Temperature influence on yield of 3a with optimized stoichiometry.[a]

I

mCPBA,

I OTf

1a 2a 3a

TfOH, CH2Cl2

Entry T (˚C) Yield (%)[b]

1 -78 38 2 -50 87 3 -25 87 4 0 91 5 rt 92 6 40 91 7 50 90 8 60 90 9 70 90 10 80 89 11 90 89

[a] Reaction conditions: mCPBA (65% active oxidant, 66 mg, 0.25 mmol) and iodobenzene (1a, 0.23 mmol) were dissolved in CH2Cl2 (1 mL) in a sealed tube. Benzene (2a, 0.25 mmol) was added and the solution was cooled to 0 ˚C for reactions run at/over 0 ˚C; in the others at the tabulated temperature, followed by dropwise addition of TfOH (62 μL, 0.69 mmol). The reaction was stirred at the indicated temperature for 10 min. [b] Isolated yield.

1.2 Synthesis of diaryliodonium salts directly from arenes and iodine. Direct application of the previously optimized reaction conditions but with 3 equiv. mCPBA[1] indeed resulted in formation of salt 3a (Table S3, entry 1). The use of 4 equivalents of mCPBA improved the conversion, and resulted in a clean formation of salt 3a in 60 % yield (entry 6). The yield could be improved by prolonged reaction time or using an excess of benzene, as depicted in entries 7, 10. When the temperature was increased to 80 °C, a reaction time of 10 min was sufficient to give 3a in 93% yield (entry 13). The use of substoichiometric amount of mCPBA, with the aim of using only one iodine atom in the reaction, proved inferior and delivered 3a in only 33% yield (entry 21).[2] Table S3. Synthesis of diaryliodonium salts directly from arenes.[a]

PhH + I2

mCPBA

TfOH, CH2Cl2

Ph2I+ -OTf

2a 3a

Entry 2a (equiv.)

mCPBA (equiv)

TfOH (equiv.)

T (ºC)

Time Yield (%)[b]

1 4.1 3 4 rt 10 min 45 2 4.1 3 4 rt 12 h 58 3 4.1 3 4 rt 20 h 61 4 4.1 4 3 rt 16 h 13 5 4.1 3 6 rt 10 min 92 6 4.1 4 4 rt 2 h 60 7 4.1 4 4 rt 21 h 72 8 4.1 4 4 rt 10 min 41 9 10 4 4 rt 10 min 64 10 10 4 4 rt 22 h 81 11 10 4 4 40 10 min 75 12 4.1 3 4 60 10 min 92 (87)

S4

13 4.1 3 4 80 10 min 93 (80) 14 4.1 3 3 80 10 min 46 15 10 3 4 80 10 min 85 (78) 16 4.1 4 4 80 10 min 78 17 10 4 4 80 10 min 76

18[c] 10 3 3 80 10 min (51) 19[c] 10 4 4 80 10 min (66) 20[c] 10 6 6 80 10 min (72) 21 4.1 2.1 3 rt 22 h 33

[a] Reaction conditions: mCPBA (65% active oxidant) and iodine were dissolved in CH2Cl2 in a sealed tube. Benzene (2a) was added and the solution was cooled to 0 ˚C for reactions run at/over 0 ˚C; in the others at the tabulated temperature, followed by dropwise addition of TfOH. [b] Isolated yield. ( ) are isolated by flash chromatography.

2 Reaction conditions for the synthesis of salts 3

General experimental conditions NMR spectra were recorded using DMSO-d6, CDCl3 or MeOD-d4 as solvent. DMSO-d6 was used in most cases, as all iodonium salts were soluble in this solvent. Chemical shifts are given in ppm relative to TMS for CDCl3, the residual peak of DMSO (1H NMR δ 2.50, 13C NMR 39.52) or MeOD (1H NMR δ 3.31, 13C NMR 49.00) as internal standard, with multiplicity (s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet, br=broad, app=apparent), integration and coupling constants (Hz). In the IR spectra, only the strongest/structurally most important peaks are listed. The reactions were carried out in sealed tubes to allow for reaction temperatures above the boiling point of CH2Cl2. The reactions were run without precaution to avoid moisture or air, i.e. without protective gas or dried solvent. TfOH (≥99%) was stored under argon atmosphere. The percentage of active oxidizing agent in mCPBA was determined by iodometric titration.[3] All other chemicals were used as received without further purification. Analytical details of all novel salts are given in the supporting information. General synthetic procedures are given in the Experimental part. Tables S4 and S5 give details on reaction times and temperatures, which have not been optimized for each product but roughly anticipated from the electronic properties of the substrates. The reactions were generally performed with 2 equiv. triflic acid, unless this resulted in byproduct formation. Flash chromatography was performed with a CH2Cl2/MeOH gradient from 50:1 to 10:1. Table S4: Reaction conditions for the synthesis of salts 3 from aryl iodides and arenes.

Ar1-I + Ar2-HmCPBA,

TfOH, CH2Cl2

IAr1 Ar2

OTf

1 2 3 Entry Ar1I Ar2H TfOH

(equiv) T (˚C) Time Product Yield

(%)[a]

1 1a 2a 3 rt 10 min 3a 92 2 1a 2b 2 80 2 h 3b 85 3 1a 2c 3 rt 22 h 3c 71[b] 4 1a 2d 3 rt 17 h 3d 57[b] 5 1a 2e 3 rt 1 h 3e 92[b] 6 1a 2f 2 0 10 min 3f 85 7 1a 2g 2 0rt 1 h 3g 86 8 1a 2h 2 rt 3 h 3h 66

S5

9 1a 2i 3 0 1 h 3i 80 10 1a 2j 2 rt 1 h 3j 78 11 1a 2k 2 0rt 1 h 3k’:3k’’1.2:1 94 12 1a 2l 2 rt 1 h 3l 83 13 1a 2m 2 rt / -78 10 + 10 min 3m 87 14 1a 2n 2 rt / 0 10 + 15 min 3n 82 15 1b 2a 3 0 1 h 3c 78 16 1b 2c 3 0 1 h 3o 91 17 1b 2m 2 0 / -20 40 + 10 min 3p 58 18 1c 2a 3 rt 1 h 3d 65 19 1c 2d 3 rt 19 h 3q 83 20 1c 2m 2 rt / -20 60 + 10 min 3r 57 21 1d 2a 2 rt 10 min 3s 85 22 1d 2e 2 rt 24 h 3t 82 23 1d 2f 2 rt 10 min 3u 90 24 1d 2g 2 rt 1 h 3v 89 25 1d 2h 2 80 15 min 3w 62 26 1d 2i 2 0 1 h 3x 51[c] 27 1d 2j 2 rt 1 h 3y 84 28 1d 2m 3 -20 10 min 3z 56[c]

29 1e 2a 3 0 45 min 3f 71 30 1e 2f 2 rt 10 min 3aa 52 31 1f 2a 2 rt 1 h 3g 66[c] 32 1g 2a 2 80 15 h 3ab 85 33 1h 2a 2 80 15 h 3ac 59 34 1i 2a 2 80 15 h 3ad 63 35 1j 2a 2 0 1 h 3ae 73 36 1k 2a 3 80 2 h 3af 60 37 1k 2m 3 0 15 min 3ag 53

[a] Isolated yield. [b] About 5% ortho-isomer detectable by NMR. [c] Isolated by flash chromatography. Table S5. Reaction conditions for the reaction of arenes 2 with iodine.

4 Ar-H + I2

mCPBA,

TfOH, CH2Cl2

IAr Ar

OTf

32 Entry ArH /

(equiv) T (˚C) Time Product Yield

(%)[a]

1[b] 2a / 4.1 80 10 min 3a 93 2 2a / 10 rt 22 h 3a 81 3 2c / 10 rt 20 min 3o 64 4 2d / 10 rt 21 h 3q 57 5 2e / 10 rt 12 h 3ah 71 6 2f / 10 rt 2 h 3u:3aa 3:1 52 7 2f / 4.1 0 1 h 3u 31 8 2g / 10 rt 10 min 3ai 78 9 2h / 10 rt 12 h 3aj 47

10[b] 2j / 4.1 rt 1 h 3ak 52 11 2o / 10 rt 19 h 3al 24

[a] Isolated yield. [b] 3 equiv. mCPBA was used.

S6

3 Analytical data of diaryliodonium salts 3 Diphenyliodonium triflate (3a):[4-6]

I OTf

3a Synthesized from PhI + PhH in 92% yield or from PhH + I2 in 81% yield. Analytical data were in agreement with previous reports. (4-Iodophenyl)(phenyl)iodonium triflate (3b):[5, 6]

IOTf

3bI

Synthesized from PhI + PhI in 85% yield as a white solid. Analytical data were in agreement with previous reports. (4-Bromophenyl)(phenyl)iodonium triflate (3c):[6]

IOTf

3cBr

Synthesized from 4-BrPhI + PhH in 78% yield or from PhI + PhBr in 71% as a white solid. Analytical data were in agreement with previous reports. (4-Chlorophenyl)(phenyl)iodonium triflate (3d):[6]

IOTf

3dCl

Synthesized from 4-ClPhI + PhH in 65% yield or from PhI + PhCl in 57% as a white solid. Analytical data were in agreement with previous reports. (4-Fluorophenyl)(phenyl)iodonium triflate (3e):[6]

IOTf

3eF

Synthesized from PhI + PhF in 92% yield as a white solid. Analytical data were in agreement with previous reports. (4-Methylphenyl)(phenyl)iodonium triflate (3f):[5, 7]

IOTf

3f Synthesized from PhI + PhMe in 85% yield or from 4-MePhI + PhH in 71% yield as an off-white solid. The 13C NMR given in reference 7 is in accordance with our data, whereas the 1H NMR differs. mp: 120-121 ˚C (lit7: 122-125 ˚C); 1H NMR (400 MHz, DMSO-d6): δ 8.21 (d, J = 7.6 Hz, 2H), 8.12 (d, J = 8.2 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.52 (t, J = 7.6 Hz, 2H), 7.34 (d, J = 8.2 Hz, 2H), 2.34 (s, 3H); IR (film): 3082, 3060, 2922, 1258, 1170, 1026 cm-1. (4-tert-Butylphenyl(phenyl)iodonium triflate (3g):[6]

S7

IOTf

3g tBu Synthesized from PhI + PhtBu in 86% yield or from 4-tBuPhI + PhH in 66% as a white solid. Analytical data were in agreement with previous reports. (2,5-Dimethylphenyl)(phenyl)iodonium triflate (3h):[8]

IOTf

3h

Synthesized from PhI + p-xylene in 66% yield as a off-white solid. Analytical data were in agreement with previous reports. (2,5-Di-tert-butylphenyl)(phenyl)iodonium triflate (3i):

IOTf

3i

tBu

tBu Synthesized from PhI and 1,4-tBu2Ph in 80% yield as a white solid. mp: 160-161 ˚C; 1H NMR (400 MHz, MeOD-d4): δ 8.40 (s, 1H), 8.01 (d, J = 8.42 Hz, 2H), 7.73 (s, 2H), 7.68 (t, 7.44 Hz, 1H), 7.55 (app. t, J = 7.80 Hz, 2H), 1.53 (s, 9H), 1.34 (s, 9H); 13C NMR (100 MHz, MeOD-d4): δ 155.2, 149.2, 140.0, 135.1, 133.6, 133.3, 131.2, 130.7, 121.8 (q, J = 316.4 Hz, CF3SO3

–), 117.0, 116.0, 38.1, 35.8, 31.9, 31.2; IR (film): 2922, 1263, 1173, 1028 cm-1; HRMS (ESI): calcd for C20H26I ([M – TfO–]+): 393.1074; found 393.1066. (2,4,6-Trimethylphenyl)(phenyl)iodonium triflate (3j):[7]

IOTf

3j Synthesized from PhI + mesitylene in 78% yield as a white solid. Analytical data were in agreement with previous reports. (1-Bromo-4,6-dimethylphenyl)(phenyl)iodonium triflate (3k’) and (2,6-dimethyl-4-bromophenyl)(phenyl)iodonium triflate (3k’’):

IOTf

3k'

Br

IOTf

3k''Br

Synthesized from PhI + 3,5-Me2PhBr in 94% yield as a regioisomeric mixture. Ratio 3k’:3k’’ = 1.2:1. 1H NMR (400 MHz, MeOD-d4): 3k’: 8.08 (d, J = 7.6 Hz, 2H), 7.71-7.65 (m, 1H), 7.63 (s, 1 H), 7.57-7.51 (m, 2 H), 7.38 (s, 1 H), 2.78 (s, 3 H), 2.37 (s, 3 H). 3k’’: δ 7.96 (d, J = 7.6 Hz, 2 H), 7.71-7.65 (m, 1H), 7.63 (s, 2 H), 7.57-7.51 (m, 2 H), 2.70 (s, 6 H). (4-Acetoaminophenyl)(phenyl)iodonium triflate (3l):[8]

IOTf

3lNHAc

Synthesized from PhI + acetanilide in 83% yield as a white solid. mp: 175-177 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 10.30 (br, 1 H), 8.18 (dd, J = 8.2, 1.0 Hz, 2 H), 8.16 (d, J = 9.0 Hz,

S8

2 H), 7.69 (d, J = 9.0 Hz, 2 H), 7.65 (t, J = 7.6 Hz, 1 H), 7.52 (app t, J = 7.7 Hz, 2 H), 2.06 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ 169.1, 142.6, 136.3, 134.8, 131.9, 131.7, 121.4, 116.8, 107.7, 24.1; 19F NMR (376 MHz, DMSO-d6): δ -77.7; IR (CHCl3): 3316.7, 3183.1, 1681.1, 1530.5, 1216.8, 1182.7, 1029.3 cm-1; HRMS (ESI): calcd for C14H13INO ([M – TfO-

]+): 338.0036; found 338.0041. (4-Methoxyphenyl)(phenyl)iodonium triflate (3m):[4, 5, 7]

IOTf

3mOMe

Synthesized from PhI + PhOMe in 87% yield. Analytical data were in agreement with previous reports. (2-Thienyl)(phenyl)iodonium triflate (3n):[5, 9]

I OTf

3n

S

Synthesized from PhI + thiophene in 82% yield. Analytical data were in agreement with previous reports. Bis(4-bromophenyl)iodonium triflate (3o):[10-12]

IOTf

3oBr Br Synthesized from 4-BrPhI + PhBr in 91% yield or from PhBr + I2 in 64% yield. Our analytical data match reference 11 but 1H NMR is not in agreement with reference 10. mp: 203 ˚C (decomposed); 1H NMR (400 MHz, DMSO-d6): δ 8.17 (d, J = 8.6 Hz, 4 H), 7.77 (d, J = 8.6 Hz, 4 H); 13C NMR (100 MHz, CD3OD): δ 138.1, 136.3, 128.8, 121.8 (q, J = 318.5 Hz, CF3SO3

–), 114.5; IR (film): 3084, 1471, 1260, 1173, 1028 cm-1; HRMS (ESI): calcd for C12H8Br2I ([M – TfO-]+): 436.8032; found 436.8041. (4-Bromophenyl)(4-methoxyphenyl)iodonium triflate (3p):

IOTf

3pBr OMe Synthesized from 4-BrPhI + PhOMe in 58% yield as a grey solid. mp: 143-144 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.17 (d, J = 9.0 Hz, 2H), 8.12 (d, J = 8.6 Hz, 2H), 7.74 (d, J = 8.6 Hz, 2H), 7.08 (d, J = 9.0 Hz, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 162.1, 137.3, 136.7, 134.5, 126.0, 120.7 (q, J = 322.1 Hz, CF3SO3

–), 117.5, 115.5, 105.6, 55.7; IR (film): 3084, 1572, 1488, 1259, 1175, 1028 cm-1; HRMS (ESI): calcd for C13H11BrOI ([M – TfO–]+): 388.9032; found 388.9022. Bis(4-chlorophenyl)iodonium triflate (3q):[5, 10]

IOTf

3qCl Cl Synthesized from 4-ClPhI + PhCl in 83% yield or from PhCl + I2 in 57% yield as a single regioisomer. Our analytical data are not in agreement with reference 10. mp: 181-183 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.26 (d, J = 8.6 Hz, 4H), 7.63 (d, J = 8.6 Hz, 4H); 13C NMR (100 MHz, CDCl3): δ 139.8, 136.8, 132.5, 120.0 (q, J = 318 Hz, CF3SO3

–), 111.2; IR (film):

S9

3086, 1260, 1172, 1026 cm-1; HRMS (ESI): calcd for C12H8Cl2I ([M – TfO–]+): 348.9042; found 348.9041. (4-Chlorophenyl)(4-methoxyphenyl)iodonium triflate (3r):

IOTf

3rCl OMe Synthesized from 4-ClPhI + PhOMe in 57% yield as a grey solid. mp: 129-130 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.19 (app. t, J = 8.9 Hz, 4H), 7.61 (d, J = 8.6 Hz, 2H), 7.08 (d, J = 8.9 Hz, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 162.1, 137.2, 137.1, 136.6, 131.6, 120.7 (q, J = 322.4 Hz), 117.5, 114.8, 105.6, 55.7; IR (film): ): 3087, 1572, 1488, 1258, 1175, 1028 cm-1; HRMS (ESI): calcd for C13H11ClOI ([M – TfO–]+): 344.9538; found 344.9534. (2-Methylphenyl)(phenyl)iodonium triflate (3s):[5, 13]

IOTf

3s Synthesized from 2-MePhI + PhH in 85% yield as an off-white solid. mp: 162-164˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.39 (d, J = 7.8 Hz, 1H), 8.20 (d, J = 7.7 Hz, 2H), 7.66 (t, J = 7.4 Hz, 1H), 7.57 (m, 2H),7.51 (t, J = 7.7 Hz, 2H), 7.32 (t, J = 6.2 Hz, 1H), 2.61 (s, 3H); 13C NMR (100 MHz, DMSO-d6): 140.6, 137.1, 135.0, 132.9, 132.0, 131.8, 131.4, 129.3, 121.4, 120.7 (q, J = 320 Hz, CF3SO3

–), 115.9, 25.0; HRMS (ESI): calcd for C13H12I ([M – TfO–]+): 294.9978; found 294.9985. (2-Methylphenyl)(4-fluorophenyl)iodonium triflate (3t):

I OTf

3tF

Synthesized from 2-MePhI + PhF in 82% yield. mp: 161-162 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.40 (d, J = 8.0 Hz, 1 H), 8.27-8.30 (m, 2 H), 7.55-7.61 (m, 2 H), 7.40 (t, J = 8.7 Hz, 2 H), 7.32 (t, J = 7.1 Hz, 1 H), 2.62 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ 163.9 (d, J = 351.7 Hz), 140.54, 137.9 (d, J = 8.8 Hz), 137.0, 132.9, 131.5, 129.3, 121.8, 120.7 (q, J = 322.7 Hz, CF3SO3), 119.2 (d, J = 22.8 Hz), 110.0 (d, J = 3.1 Hz), 25.0; 19F NMR (376 MHz, DMSO-d6): δ -77.7, -106.8; IR (film): 3092.7, 3055.4, 1634.1, 1574.9, 1482.1, 1268.5, 1253.9, 1236.5, 1163.4, 1026.2 cm-1; HRMS (ESI): calcd for C13H11FI ([M – TfO–]+): 312.9884; found 312.9888. (2-Methylphenyl)(4-methylphenyl)iodonium triflate (3u):[5, 14]

IOTf

3u Synthesized from 2-MePhI + PhMe in 87% yield; from PhMe + I2 as a regioisomeric mixture with 3aa (ratio 3u:3aa 3:1) in 52% combined yield or as the single regioisomer in 31% yield. Analytical data were in agreement with previous reports. 1H NMR (400 MHz, DMSO-d6): δ 8.36 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 8.6 Hz, 2H), 7.57 (m, 2H), 7.32 (m, 3H) 2.60 (s, 3H), 2.33 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 142.5, 140.5, 137.0, 135.0, 132.8, 132.4,

S10

131.4, 129.3, 121.5, 120.7 (q, J = 321 Hz, CF3SO3–), 112.2, 25.0, 20.8; HRMS (ESI): calcd

for C14H14I ([M – TfO–]+): 309.0135; found 309.0140. (2-Methylphenyl)(4-tert-butylphenyl)iodonium triflate (3v):[14]

IOTf

3v tBu Synthesized from 2-MePhI + PhtBu in 89% yield as a white solid. mp: 168-170 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.40 (d, J = 8.0 Hz, 1 H), 8.11 (d, J = 8.4 Hz, 2H), 7.60-7.52 (m, 4 H), 7.31 (app. t, 1 H), 2.62 (s, 3 H), 1.25 (9 H); 13C NMR (100 MHz, DMSO-d6): δ 155.2, 140.5, 137.1, 134.8, 132.8, 131.4, 129.3, 128.9, 121.3, 120.7 (q, J = 320.3 Hz, CF3SO3

–), 119.1, 115.9, 112.3, 34.9, 30.7, 25.0; IR (CHCl3): 2971, 2907, 1259, 1173, 1028 cm-1; HRMS (ESI): calcd for C17H20I ([M – TfO–]+): 351.0604; found 351.0601. (2-Methylphenyl)(2,5-dimethylphenyl)iodonium triflate (3w):

IOTf

3w

Synthesized from 2-MePhI + p-xylene in 62% yield as a white solid. mp: 140-141 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.28 (d, J = 8.0 Hz, 1H), 8.16 (s, 1H), 7.60-7.55 (m, 2H), 7.43 (d, J = 7.8 Hz, 1H), 7.39 (d, J = 7.8 Hz, 1 H), 7.32-7.28 (m, 1 H), 2.61 (s, 3H), 2.55 (s, 3H), 2.30 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 140.6, 139.1, 137.4, 137.1, 133.4, 132.7, 131.6, 131.2, 129.3, 120.7 (q, J = 320.3 Hz, CF3SO3

-), 120.3, 120.2, 25.0, 24.4, 20.0; IR (CHCl3): 2925, 12578, 1173, 1036, 1027 cm-1; HRMS (ESI): calcd for C15H16I ([M – TfO–]+): 323.0291; found 323.0301. (2-Methylphenyl)(2,5-bis(tert-butyl)phenyl)iodonium triflate (3x):

IOTf

3x

tBu

tBu Synthesized from 2-MePhI + 1,4-tBu2Ph in 51% yield as a white solid. mp: 102-103 ˚C; 1H NMR (400 MHz, CDCl3): δ 8.03 (dd, J = 8.1, 1.1 Hz, 1H), 7.65 (td, J = 7.6, 1.1 Hz, 1H), 7.58 (d, J = 8.4 Hz, 1H), 7.57 (m, 1H), 7.46 (dd, J = 8.4, 2.0 Hz, 1H), 7.35 (t, J = 7.7 Hz, 1H), 7.27 (d, J = 2.0 Hz, 1 H); 2.59 (s, 3 H), 1.55 (s, 9 H), 1.07 (s, 9 H); 13C NMR (100 MHz, CDCl3): δ 153.7, 147.4, 141.5, 137.9, 134.0, 132.5, 131.5, 130.0, 129.7, 128.8, 120.4 (q, J = 320.7 Hz, CF3SO3

–), 120.0, 112.3, 36.3, 34.6, 31.2, 30.6, 25.7; IR (film): 3085, 2965, 2873, 1596, 1480, 1460, 1260, 1157, 1028 cm-1; HRMS (ESI): calcd for C21H28I ([M – TfO–]+): 407.1230; found 407.1238. (2-Methylphenyl)(2,4,6-trimethylphenyl)iodonium triflate (3y):

IOTf

3y Synthesized from 2-MePhI + mesitylene in 84% yield as a white solid. mp: 164-166 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 7.95 (d, J = 8 Hz), 7.58-7.55 (m, 2 H), 7.28-7.24 (m, 1 H), 7.21 (s, 2 H), 2.57-2.56 (m, 9 H), 2.29 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ 143.0, 141.6, 140.7, 136.7, 132.4, 131.9, 129.9, 129.3, 121.8, 120.7 (q, J = 320.6 Hz, CF3SO3

–),

S11

118.6, 26.1, 24.4, 20.4; IR (CHCl3): 2922, 1262, 1173, 1037, 1028 cm-1; HRMS (ESI): calcd for C16H18I ([M – TfO–]+): 337.0448; found 337.0453. (2-Methylphenyl)(4-methoxyphenyl)iodonium triflate (3z):

I OTf

3zOMe

Synthesized from 2-MePhI + anisole in 56% yield as a white solid. mp: 171-172 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 8.36 (dd, J = 7.9, 1.0 Hz, 1 H), 8.13 (dt, J = 9.2 Hz, 2 H), 7.52-7.58 (m, 2 H), 7.28-7.32 (m, 1 H), 7.05 (dt, J = 9.2 Hz, 2 H), 3.79 (s, 3 H), 2.61 (s, 3 H); 13C NMR (100 MHz, DMSO-d6): δ 161.9, 140.3, 137.1, 136.8, 132.7, 131.3, 129.2, 121.9, 120.7 (q, J = 322.4 Hz), 117.5, 104.8, 55.7, 24.9; 19F NMR (376 MHz, DMSO-d6): δ -77.7; IR (film): 3089.5, 2924.0, 1572.9, 11488.1, 1258.8, 1175.5, 1026.5 cm-1; HRMS (ESI): calcd for C14H14IO ([M – TfO–]+): 325.0084; found 325.0092. Bis(4-methylphenyl)iodonium triflate (3aa):[5, 15]

IOTf

3aa Synthesized from 4-MePhI + toluene in 52% yield as an off-white solid. The 13C NMR given in reference 15 is in accordance with our data, whereas the 1H NMR differs. 1H NMR (400 MHz, DMSO-d6): δ 8.08 (d, J = 8.0 Hz, 4H), 7.32 (d, J = 8.0 Hz, 4H), 2.34 (s, 6H); 13C NMR (100 MHz, DMSO-d6): δ 142.5, 135.0, 132.3, 120.7 (q, J = 320 Hz, CF3SO3

–), 113.0, 20.8; HRMS (ESI): calcd for C14H14I ([M – TfO–]+): 309.0135; found 309.0131. (4-Nitrophenyl)(phenyl)iodonium triflate (3ab):[5, 6]

IOTf

3abO2N Synthesized from 4-NO2PhI + PhH in 85% yield as a white solid. Analytical data were in agreement with previous reports. (4-Trifluoromethylphenyl)(phenyl)iodonium triflate (3ac):

IOTf

3acF3C Synthesized from 4-CF3PhI + PhH in 59% yield as a white solid. mp: 120-122 ˚C; 1H NMR (400 MHz, MeOD-d4): δ 8.37 (d, J = 8.4 Hz, 2H), 8.24 (d, J = 8.3 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.73 (t, J = 7.6 Hz, 1H), 7.57 (app. t, J = 7.8 Hz, 2H); 13C NMR (100 MHz, MeOD-d4): δ 135.7, 135.3, 133.7 (q, J = 33.0 Hz), 132.6, 132.0, 128.3 (q, J = 3.7 Hz), 123.3 (q, J = 270.6 Hz), 120.4 (q, J = 316.0 Hz), 118.4, 114.8; IR (film): 3091, 1595, 1259, 1173, 1028 cm-

1; HRMS (ESI): calcd for C13H9F3I ([M – TfO-]+): 348.9696; found 348.9681. (3-Trifluoromethylphenyl)(phenyl)iodonium triflate (3ad):[6]

IOTf

3ad

F3C

Synthesized from 3-CF3PhI + PhH in 63% yield as a white solid. Analytical data were in agreement with previous reports.

S12

(4-Carboxyphenyl)(phenyl)iodonium triflate (3ae): I

OTf

3aeHOOC Synthesized from 4-(COOH)PhI + PhH in 73% yield as a off-white solid. mp: 175-176 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 13.50 (s, 1H), 8.34 (d, J = 8.6 Hz, 2H), 8.27 (d, J = 7.2 Hz, 2H), 8.00 (d, J = 8.6 Hz, 2H), 7.69 (t, J = 7.6 Hz, 1H), 7.55 (app. t, J = 7.8 Hz, 2H); 13C NMR (100 MHz, DMSO-d6): δ 166.1, 135.4, 133.9, 132.2, 132.1, 131.9, 120.8, 120.7 (q, J = 320.1 Hz), 116.6; IR (CHCl3): 3020 (br), 2823, 1715, 1582, 1259, 1173, 1037 cm-1; HRMS (ESI): calcd for C13H10IO2 ([M – TfO–]+): 324.9720; found 324.9710. (6-Chloro-pyridin-3-yl)(phenyl)iodonium triflate (3af):[5, 16]

N

IOTf

3afCl Synthesized from 2-chloro-5-iodopyridine + PhH in 60% yield as a white solid. mp: 153-155 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 9.17 (d, J = 2.3 Hz, 1H), 8.70 (dd, J = 8.5, 2.3 Hz, 1H), 8.28 (d, J = 7.6 Hz, 2H), 7.75 (d, J = 8.5 Hz, 1H), 7.70 (t, J = 7.6 Hz, 1H), 7.56 (t, J = 7.6 Hz, 2H); 13C NMR (100 MHz, DMSO-d6): δ 154.3, 153.4, 145.5, 135.2, 132.4, 132.0, 127.6, 120.7 (q, J = 322 Hz, CF3SO3

–), 116.9, 114.2; IR (film): 3084, 3055, 1554, 1445, 1260, 1172, 1027 cm-1; HRMS (ESI): calcd for C11H8ClIN ([M – TfO–]+): 315.9384; found 315.9393. (6-chloro-pyridin-3-yl)(4-methoxyphenyl)iodonium triflate (3ag):[5]

N

I OTf

3agCl OMe Synthesized from 2-chloro-5-iodopyridine + PhOMe in 53% yield. mp: 101-103 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 9.12 (d, J = 2.1 Hz, 1H), 8.64 (dd, J = 8.5, 2.1 Hz, 1H), 8.20 (d, J = 8.9 Hz, 2H), 7.72 (d, J = 8.5 Hz, 1H), 7.10 (d, J = 8.9 Hz, 2H) 3.80 (s, 3H); 13C NMR (100 MHz, DMSO-d6): δ 162.2, 154.0, 153.2, 145.3, 137.3, 127.5, 120.7 (q, J = 321 Hz, CF3SO3

–), 117.7, 114.6, 105.7, 55.8; IR (film): 3090, 3047, 1572, 1443, 1258, 1172, 1026 cm-1; HRMS (ESI): calcd for C12H10ClINO ([M – TfO–]+): 345.9490; found 345.9501. Bis(4-fluorophenyl)iodonium triflate (3ah):[10]

I OTf

3ahF F Synthesized from PhF + I2 in 71% yield. The 13C NMR given in reference 10 is in accordance with our data, whereas the 1H NMR differs. mp: 101 ˚C (decomposed); 1H NMR (400 MHz, CD3OD): δ 8.26-8.21 (m, 4 H), 7.34-7.27 (m, 4 H); 13C NMR (100 MHz, CD3OD): δ 166.5 (d, J = 255.5 Hz), 139.3 (d, J = 8.9 Hz), 121.8 (q, J = 318.6 Hz, CF3SO3

–), 120.6 (d, J = 23.1 Hz), 110.2 (J = 2.3 Hz); IR (CHCl3): 2977, 2920, 1636, 1260, 1174, 1036 cm-1; HRMS (ESI): calcd for C12H8F2I ([M – TfO-]+): 316.9633; found 316.9632. Bis(4-tert-butylphenyl)iodonium triflate (3ai):[4, 10]

I OTf

3aitBu tBu Synthesized from t-butylbenzene + I2 in 78% yield. The NMR data given in reference 10 are not accordance with our data. mp: 153-155 ˚C; 1H NMR (400 MHz, CDCl3): δ 7.90 (dt, J =

S13

8.9, 2.5 Hz, 4H), 7.45 (dt, J = 8.9, 2.5 Hz, 4H), 1.29 (s, 18H); 13C NMR (100 MHz, CDCl3): δ 156.5, 134.9, 129.6, 120.2 (q, J = 320.5 Hz, CF3SO3

–), 109.4, 35.2, 30.9; IR (film): 2966, 2907, 2871, 1643, 1254, 1163, 1030 cm-1; HRMS (ESI): calcd for C20H26I ([M – TfO-]+): 393.1074; found 393.1066. Bis(2,5-dimethylphenyl)iodonium triflate (3aj):

IOTf

3aj

Synthesized from p-xylene + I2 in 43% yield. mp: 173-175 ˚C; 1H NMR (400 MHz, CDCl3): δ 7.74 (m, 2 H), 7.33 (m, 4 H), 2.56 (s, 6 H), 2.34 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ 140.3, 138.0, 136.8, 134.2, 131.8, 120.3 (q, J = 320.9 Hz, CF3SO3

–), 116.9, 24.9, 20.6; 19F NMR (376 MHz, CDCl3): δ -78.4; IR (film): 2924, 1645, 1271, 1159, 1030 cm-1; HRMS (ESI): calcd for C16H18I ([M – TfO-]+): 337.0448; found 337.0444. Bis(2,4,6-trimethylphenyl)iodonium triflate (3ak):[12, 14]

IOTf

3ak Synthesized from mesitylene + I2 in 24% yield. mp: 187-188 ˚C (decomposed); 1H NMR (400 MHz, CDCl3): δ 7.04 (s, 4 H), 2.50 (s, 12 H), 2.32 (s, 6 H); 13C NMR (100 MHz, CDCl3): δ 143.80, 142.2, 130.9, 120.4 (q, J = 320.3 Hz, CF3SO3

–), 117.2, 26.1, 20.9; IR (CHCl3): 2925, 1636, 1453, 1256, 1166, 1030 cm-1; HRMS (ESI): calcd for C18H22I ([M – TfO-]+): 365.0761; found 365.0757. Bis(2,4-dimethyl-5-nitrophenyl)iodonium triflate (3al):[5]

IOTf

3al

NO2NO2 Synthesized from 2,4-Me2-nitrobenzene + I2 in 24% yield as a single regioisomer. mp: 200-202 ˚C; 1H NMR (400 MHz, DMSO-d6): δ 9.10 (s, 2H), 7.70 (s, 2H), 2.65 (s, 6H), 2.53 (s, 6H); 13C NMR (100 MHz, DMSO-d6): δ 147.5, 146.4, 137.9, 135.1, 132.9, 120.7 (q, J = 320 Hz, CF3SO3

–), 117.4, 24.7, 19.6; IR (film): 3095, 1523, 1342, 1261, 1173, 1024 cm-1; HRMS (ESI): calcd for C16H16IN2O4 ([M – TfO–]+): 427.0149; found 427.0145.

S14

4 Limitations to the developed protocol

PhI + ArHmCPBA,

TfOH, CH2Cl2

IPh Ar

OTf

1a 2 3

x

Br

Br

Br

Br Br

O2N

MeO

OMe OMeMeO OMe

OMe

Cl

Cl

N Cl

O2N

O

H

O

OH

O

CF3

NMe2

HN

Scheme 1. Arenes that gave no or poor yield of the desired iodonium salts with iodobenzene.

Ar1-I + Ar2-H

IAr1 Ar2

OTf

1 2 3

mCPBA,

TfOH, CH2Cl2x

S

I

I

COOH O2N

I

NO2

OMeMeO

I

; ;

;

I

Scheme 2. Aryl iodide and arene combinations that gave no or poor yield of the desired iodonium salts.

Ar-H + I2

mCPBA,

TfOH, CH2Cl2

IAr Ar

OTf

32

x

tBu

tBuBr

F3C

Cl Cl

Cl

Br

Br

Br

Br N

O

OH OH

Cl

Scheme 3: Substrates that gave no or poor yield in reactions with iodine. References [1] Complete transformation of iodine to two iodine(III) molecules would require 3 equivalents of mCPBA. [2] Iodobenzene was detected in reactions with short reaction time, supporting the assumption that iodobenzene is an intermediate in the reaction. [3] A. I. Vogel, B. S. Furniss, A. J. Hannaford, V. Rogers, P. W. G. Smith, A. R. Tatchell, Vogel's Textbook of Practical Organic Chemistry. 1978; p 1280 pp.

S15

[4] Commercially available. [5] M. Bielawski, B. Olofsson, Chem. Commun. 2007, 2521-2523. [6] M. D. Hossain, T. Kitamura, Tetrahedron 2006, 62, 6955-6960. [7] T. Kitamura, J. Matsuyuki, K. Nagata, R. Furuki, H. Taniguchi, Synthesis 1992, 945-946. [8] P. Kazmierczak, L. Skulski, Bull. Chem. Soc. Jpn. 1997, 70, 219-224. [9] D. Bykowski, R. Mcdonald, R. J. Hinkle, R. R. Tykwinski, J. Org. Chem. 2002, 67, 2798-2804. [10] M. D. Hossain, T. Kitamura, J. Org. Chem. 2006, 71, 9903-9905. [11] J. Ermert, C. Hocke, T. Ludwig, R. Gail, H. H. Coenen, J Label Compd Radiopharm 2004, 47, 429-441. [12] P. J. Stang, V. V. Zhdankin, R. Tykwinski, N. S. Zefirov, Tetrahedron Lett. 1991, 32, 7497-7498. [13] M. A. Carroll, V. W. Pike, D. A. Widdowson, Tetrahedron Lett. 2000, 41, 5393-5396. [14] A. Shah, V. W. Pike, D. A. Widdowson, J. Chem. Soc., Perkin Trans. 1 1997, 2463-2465. [15] J. L. Dektar, N. P. Hacker, J. Org. Chem. 1990, 55, 639-647. [16] V. K. Aggarwal, B. Olofsson, Angew. Chem. Int. Ed. 2005, 44, 5516-5519; ) B. Olofsson, V. K. Aggarwal, Proc. 2nd Int. Conf. on Hypervalent Iodine 2006, 47-50.

5 NMR spectra of diaryliodonium salts 3

7.47.57.67.77.87.98.08.18.28.38.4 ppm

7.515

7.534

7.554

7.652

7.670

7.689

8.238

8.257

4.027

2.062

4.000

10 9 8 7 6 5 4 3 2 1 ppm

400 MHzDMSO

O

I

SO O

CF3

7.2

7.4

7.6

7.8

8.0

8.2

8.4

8.6

ppm

7.535

7.553

7.657

7.674

7.690

7.889

7.909

7.982

8.002

8.229

8.247

1.943

1.058

3.947

2.000

10

98

76

54

32

1ppm

OI SO

O

CF3

I

400 MHz

DMSO

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

8.4

8.5

ppm

7.532

7.537

7.552

7.567

7.571

7.686

7.694

7.698

7.711

7.715

7.722

7.730

7.733

8.060

8.065

8.077

8.082

8.170

8.173

8.191

8.193

2.033

3.037

2.015

2.000

10

98

76

54

32

1ppm

I O SO

O

CF3

Br

400 MHz

MeOD

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

ppm

7.384

7.406

7.431

7.450

7.470

7.594

7.613

7.631

7.930

7.951

7.993

8.012

1.918

1.991

1.008

1.947

2.000

10

98

76

54

32

1ppm

I O SO

O

CF3

Cl

400 MHz

CDCl3

2.53.03.54.04.55.05.56.06.57.07.58.0 ppm

2.

57

2

2.

02

7

2.

00

71

.0

36

4.

00

0

7.27.37.47.57.67.77.87.98.0 ppm

7.

13

97

.1

59

7.

16

27

.1

82

7.

45

37

.4

72

7.

49

2

7.

61

47

.6

32

7.

65

1

7.

96

97

.9

72

7.

98

77

.9

91

7.

99

37

.9

99

I

3e F

S

O-

CF3

OO

400 HzCDCl3

10

98

76

54

32

1ppm

7.4

7.6

7.8

8.0

8.2

8.4

ppm

7.328

7.348

7.501

7.520

7.540

7.638

7.656

7.675

8.111

8.132

8.201

8.220

2.044

2.041

1.014

1.939

1.936

2.5

ppm

2.3393.000

400 MHz

DMSO

OI SO

O

CF3

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

ppm

7.511

7.530

7.546

7.550

7.571

7.575

7.588

7.593

7.669

7.688

7.706

8.067

8.072

8.084

8.089

8.146

8.148

8.167

8.169

2.017

2.038

1.013

2.028

2.000

1.30

1.35

ppm

1.3179.088

98

76

54

32

1ppm

I O SO

O

CF3

400 MHz

MeOD

210

200

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

0ppm

31.314

36.130

112.425

116.017

117.074

120.221

123.386

126.572

130.525

133.145

133.600

136.232

136.326

157.908

I O SO

O

CF3

100 MHz

MeOD

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

ppm

7.418

7.444

7.463

7.506

7.525

7.545

7.656

7.658

7.661

7.673

7.677

7.693

7.696

7.698

8.072

8.075

8.094

8.096

8.140

2.003

2.048

1.028

2.003

1.000

2.4

2.6

ppm

2.379

2.605

2.983

2.994

10

98

76

54

32

1ppm

I O SO

O

CF3

400 MHz

MeOD

98

76

54

32

1ppm

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

8.4

8.5

ppm

7.533

7.537

7.552

7.568

7.572

7.663

7.681

7.700

7.702

7.728

7.999

8.002

8.020

8.022

8.404

2.036

1.113

1.920

2.000

0.959

1.5

ppm

1.343

1.527

9.231

9.197

I O SO

O

CF3

400 MHz

MeOD

210

200

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

0ppm

31.247

31.932

35.774

38.070

115.955

116.960

117.043

120.207

123.372

126.535

130.675

131.161

133.278

133.562

135.057

140.041

149.197

155.204

I O SO

O

CF3

100 MHz

MeOD

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

ppm

7.221

7.481

7.500

7.516

7.520

7.614

7.617

7.619

7.631

7.635

7.639

7.651

7.654

7.656

7.961

7.964

7.982

7.985

1.996

2.036

1.015

2.000

10

98

76

54

32

1ppm

2.5

ppm

2.296

2.598

2.961

5.983

I O SO

O

CF3

400 MHz

DMSO

7.47.57.67.77.87.98.08.18.2 ppm

7.384

7.513

7.518

7.524

7.533

7.544

7.553

7.563

7.627

7.658

7.676

7.692

7.710

7.951

7.970

8.073

8.092

1.081

4.489

3.187

2.354

2.084

2.203

9 8 7 6 5 4 3 2 1 ppm

2.62.8 ppm

2.374

2.698

2.787

3.191

6.000

3.160

I

O

SO O

CF3

Br

I

O

SO O

CF3

Br

400 MHzMeOD

B A

Regioisomeric MixtureA : B ~ 1 : 1.2

A

A+B

A+B

A+B B

B

B B A

11 10 9 8 7 6 5 4 3 2 1 ppm

ppm

10

.3

04

1.

00

0

7.67.77.87.98.08.18.2 ppm

7.

50

27

.5

21

7.

54

0

7.

63

67

.6

54

7.

67

57

.6

98

8.

14

38

.1

65

8.

17

08

.1

73

8.

19

18

.1

94

5.

55

3

4.

07

3

2.02.5 ppm

2.

05

83

.1

15

I

3l NH

S OO

CF3

O-

O

400 MHzDMSO

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

110115120125130135140145 ppm

10

7.

69

5

11

6.

80

1

12

1.

40

1

13

1.

69

71

31

.8

94

13

4.

82

51

36

.3

31

14

2.

64

1

170 ppm

16

9.

10

0 ITfO-

NHAc3l

100 MHzDMSO-d6

10

98

76

54

32

1ppm

3.6

3.8

4.0

ppm

3.8013.000

6.4

6.6

6.8

7.0

7.2

7.4

7.6

7.8

8.0

8.2

8.4

8.6

ppm

6.915

6.937

7.386

7.406

7.425

7.532

7.550

7.569

7.934

7.951

7.956

7.970

2.006

2.061

1.037

4.050

400 MHz

CDCl3

OI SO

O

CF3

OMe

10

98

76

54

32

10

ppm

6.8

7.0

7.2

7.4

7.6

7.8

8.0

8.2

8.4

8.6

ppm

7.129

7.139

7.149

7.152

7.260

7.436

7.455

7.475

7.575

7.595

7.612

7.692

7.705

7.880

7.883

7.890

7.960

7.980

0.972

2.083

1.026

0.975

0.944

2.001

OI SO

O

CF3

S

400 MHz

CDCl3

10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

7.

75

67

.7

77

8.

16

18

.1

82

I

3oBr Br

S OO

CF3

O-

400 MHzDMSO

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

116118120122124126128130132134136138140 ppm

11

4.

48

8

12

0.

18

2

12

8.

75

7

13

6.

33

31

36

.3

82

13

8.

10

4

I

Br Br

TfO

3o

100 MHzCD3OD

2.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm2.

92

2.03

2.05

4.00

7.17.27.37.47.57.67.77.87.98.08.18.2 ppm

7.

07

17

.0

94

7.

73

27

.7

53

8.

10

48

.1

26

8.

15

98

.1

81

I OTf

3pBr OMe

S OO

CF3

O-

400 MHzDMSO

2030405060708090100110120130140150160170 ppm

38

.8

93

9.

10

39

.3

13

9.

52

39

.7

33

9.

94

40

.1

5

55

.7

2

10

5.

57

11

5.

52

11

7.

52

12

2.

28

12

5.

99

13

4.

52

13

6.

68

13

7.

25

16

2.

07

I OTf

3pBr OMe

S OO

CF3

O-

400 MHzDMSO

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5 ppm

7.

62

77

.6

49

8.

24

78

.2

69

4.02

4.00

I

3qCl Cl

S

O-

CF3

OO

400 HzDMSO

2.53.03.54.04.55.05.56.06.57.07.58.08.59.0 ppm

2.99

2.08

2.06

4.00

7.27.47.67.88.08.2 ppm

7.

07

27

.0

94

7.

60

17

.6

23

8.

16

18

.1

85

8.

20

7

I

3rCl OMe

S OO

CF3

O-

400 MHzDMSO

405060708090100110120130140150160170 ppm

55

.7

21

10

5.

62

3

11

4.

82

51

17

.5

23

12

2.

28

4

13

1.

62

6

13

6.

58

91

37

.2

45

16

2.

05

8

I

3rCl OMe

S OO

CF3

O-

400 MHzDMSO

98

76

54

32

1ppm

2.4

2.6

ppm

2.6134.270

6.8

7.0

7.2

7.4

7.6

7.8

8.0

8.2

8.4

8.6

8.8

9.0

ppm

7.315

7.330

7.499

7.518

7.537

7.569

7.585

7.637

7.655

7.673

8.191

8.210

8.381

8.400

1.083

4.463

1.209

2.000

1.210

OI SO

O

CF3

400 MHz

DMSO

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

7.47.67.88.08.28.4 ppm

7.

30

37

.3

19

7.

33

47

.3

73

7.

39

57

.4

17

7.

55

37

.5

70

7.

58

6

8.

26

68

.2

79

8.

28

88

.3

01

8.

38

98

.4

09

0.

98

5

1.

91

1

2.

00

0

1.

86

6

1.

03

3

2.42.52.62.7 ppm

2.

61

73

.0

88

ITfO-

F3t

400 MHzDMSO-d6

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

115120125130135140145150155160165 ppm

11

0.

01

61

10

.0

46

11

9.

13

71

19

.3

63

12

1.

77

21

22

.2

94

12

9.

32

2

13

1.

47

41

32

.9

16

13

6.

97

71

37

.8

83

13

7.

97

11

40

.5

44

16

2.

66

6

16

5.

16

7I

TfO-

F3t

100 MHzDMSO-d6

98

76

54

32

1ppm

2.4

2.6

ppm

2.330

2.604

3.047

3.073

6.8

7.0

7.2

7.4

7.6

7.8

8.0

8.2

8.4

8.6

8.8

9.0

ppm

7.311

7.330

7.555

7.572

8.071

8.090

8.352

8.372

3.098

2.210

2.000

0.895

OI SO

O

CF3

400 MHz

DMSO

10

98

76

54

32

1ppm

1.5

2.0

2.5

ppm

1.245

2.623

9.000

2.981

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

8.4

8.5

8.6

ppm

7.293

7.299

7.314

7.329

7.335

7.518

7.540

7.564

7.566

7.580

7.582

7.601

8.102

8.123

8.397

8.417

1.006

4.016

1.970

0.980

I O SO

O

CF3

400 MHz

DMSO

200

180

160

140

120

100

80

60

40

20

0ppm

115

120

125

130

135

140

145

150

155

ppm

112.27

115.88

119.09

121.34

122.29

125.49

128.93

129.29

131.41

132.82

134.81

137.06

140.54

155.18

30

35

ppm

25.03

30.68

34.87

I O SO

O

CF3

100 MHz

DMSO

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

ppm

7.279

7.286

7.294

7.300

7.314

7.321

7.380

7.400

7.426

7.445

7.548

7.561

7.577

7.579

7.598

8.162

8.279

8.299

1.038

1.987

2.051

0.948

1.000

10

98

76

54

32

1ppm

2.4

2.5

2.6

2.7

ppm

2.299

2.547

2.611

2.830

3.137

2.985

I O SO

O

CF3

400 MHz

DMSO

-10

210

200

190

180

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

20

10

0ppm

19.996

24.406

24.977

115.879

119.088

120.248

120.316

122.288

125.489

129.283

131.165

131.577

132.710

133.396

137.095

137.380

139.109

140.604

I O SO

O

CF3

100 MHz

DMSO

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

7.37.47.57.67.77.87.98.08.1 ppm

7.

26

67

.2

71

7.

31

67

.3

20

7.

33

87

.3

40

7.

35

57

.3

59

7.

44

87

.4

53

7.

46

97

.4

74

7.

55

77

.5

60

7.

57

17

.5

76

7.

57

97

.5

91

7.

62

87

.6

31

7.

64

77

.6

49

7.

66

57

.6

68

8.

01

88

.0

20

8.

03

88

.0

41

1.

02

4

1.

06

3

0.

99

4

1.

95

9

1.

02

9

1.

00

0I

TfO-

3z

400 MHzCDCl3

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

115120125130135140145150155 ppm

11

2.

26

0

11

8.

80

81

20

.0

26

12

1.

99

2

12

8.

83

91

29

.7

15

13

0.

04

31

31

.5

43

13

2.

54

41

34

.0

24

13

7.

91

9

14

1.

55

0

14

7.

37

5

15

3.

69

6

2830323436 ppm

25

.7

19

30

.6

04

31

.1

68

34

.6

33

36

.3

36

I

TfO-

3z

100 MHzCDCl3

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

ppm

7.211

7.235

7.247

7.256

7.268

7.277

7.331

7.349

7.412

7.466

7.545

7.556

7.577

7.690

7.738

7.758

7.863

7.949

7.969

2.017

1.129

2.066

1.009

10

98

76

54

32

1ppm

2.2

2.3

2.4

2.5

2.6

2.7

2.8

ppm

2.291

2.562

2.569

3.054

9.000

I O SO

O

CF3

400 MHz

DMSO

200

180

160

140

120

100

80

60

40

20

0ppm

120

125

130

135

140

145

150

ppm

115.888

118.564

119.097

121.819

122.299

125.507

129.304

129.941

131.862

132.434

136.665

140.691

141.606

142.985

18

20

22

24

26

28

30

ppm

20.424

24.390

26.128

I O SO

O

CF3

100 MHz

DMSO

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

7.27.47.67.88.08.28.4 ppm

7.

27

57

.2

77

7.

28

17

.2

83

7.

29

37

.2

95

7.

29

87

.2

99

7.

30

17

.3

03

7.

31

27

.3

13

7.

31

87

.3

19

7.

54

37

.5

47

7.

55

07

.5

64

7.

56

6

8.

12

18

.1

45

8.

34

78

.3

49

8.

36

68

.3

69

2.

01

5

1.

03

3

2.

05

2

2.

00

2

1.

00

0I

TfO

3z

400 MHzDMSO-d6

OMe

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

110115120125130135140145150155160165 ppm

10

4.

75

7

11

7.

48

7

12

1.

90

3

12

9.

19

31

31

.3

26

13

2.

67

4

13

6.

79

41

37

.0

64

14

0.

33

0

16

1.

89

8I

TfO

3z

100 MHzDMSO-d6

OMe

10 9 8 7 6 5 4 3 2 1 ppm

7.07.58.08.59.0 ppm

7.313

7.333

8.075

8.095

4.000

3.957

O

I

SO O

CF3

400 MHzDMSO

10

98

76

54

32

1ppm

7.4

7.6

7.8

8.0

8.2

8.4

8.6

8.8

ppm

7.557

7.575

7.593

7.596

7.720

7.740

7.757

8.242

8.261

8.309

8.330

8.331

8.405

8.423

8.425

1.970

1.002

1.885

2.063

2.000

OI SO

O

CF3

NO2

400 MHz

MeOD

10

98

76

54

32

1ppm

7.5

7.6

7.7

7.8

7.9

8.0

8.1

8.2

8.3

8.4

8.5

8.6

ppm

7.547

7.551

7.566

7.583

7.586

7.709

7.711

7.728

7.746

7.822

7.843

8.223

8.226

8.245

8.247

8.363

8.383

2.047

1.028

2.022

2.000

2.009I

CF3

O SO

O

CF3

400 MHz

MeOD

200

180

160

140

120

100

80

60

40

20

0ppm

114

116

118

120

122

124

126

128

130

132

134

136

138

140

ppm

114.763

115.666

118.386

118.818

119.229

121.938

121.982

124.643

125.146

127.349

128.265

128.303

128.339

128.376

131.980

132.608

133.245

133.574

133.903

134.236

135.347

135.748

I

CF3

O SO

O

CF3

100 MHz

MeOD

7.4

7.6

7.8

8.0

8.2

8.4

8.6

8.8

9.0

ppm

7.549

7.553

7.568

7.584

7.588

7.593

7.710

7.729

7.748

7.750

7.995

8.015

8.236

8.239

8.243

8.258

8.260

8.430

8.450

8.593

2.033

2.027

1.008

2.000

1.005

0.973

10

98

76

54

32

1ppm

I O SO

O

CF3

CF3

400 MHz

MeOD

15

14

13

12

11

10

98

76

54

32

1ppm

14

ppm

13.4991.018

7.6

7.8

8.0

8.2

8.4

ppm

7.528

7.548

7.567

7.668

7.686

7.705

7.995

8.017

8.266

8.284

8.329

8.350

1.984

1.018

1.984

2.020

2.000

I O SO

O

CF3

O

OH

400 MHz

DMSO

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

116.574

119.081

120.806

122.282

131.877

132.086

132.243

133.867

135.350

166.123

I

O

SO O

CF3

O

OH

100 MHzDMSO

10

98

76

54

32

1ppm

7.4

7.6

7.8

8.0

8.2

8.4

8.6

8.8

9.0

9.2

9.4

ppm

7.540

7.545

7.560

7.579

7.678

7.696

7.715

7.735

7.756

8.271

8.273

8.292

8.294

8.687

8.693

8.709

8.715

9.169

9.175

2.039

1.038

1.022

2.000

1.004

0.983

OI

N

SO

O

CF3

Cl

400 MHz

MeOD

10

98

76

54

32

1ppm

7.0

7.5

8.0

8.5

9.0

9.5

ppm

7.085

7.108

7.717

7.738

8.188

8.210

8.626

8.631

8.647

8.653

9.120

9.125

1.959

0.964

1.903

0.965

0.919

OI

N

SO

O

CF3

Cl

OMe

400 MHz

DMSO

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

7.37.47.57.67.77.87.98.08.18.28.3 ppm

7.

28

37

.3

05

7.

30

67

.3

27

8.

22

18

.2

33

8.

24

48

.2

56

4.

03

2

4.

00

0

I

F F

TfO

3ah

400 MHzCD3OD

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

105110115120125130135140145150155160165170 ppm

11

0.

21

31

10

.2

37

12

0.

20

31

20

.4

65

12

0.

69

71

23

.3

67

13

9.

22

6

16

5.

17

5

16

7.

70

5I

F F

TfO

3ah

100 MHzCD3OD

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

7.58.0 ppm

7.

44

37

.4

65

7.

88

57

.9

07

3.

98

4

4.

00

0

1.21.31.4 ppm

1.

29

21

8.

37

1

I

tBu tBu

TfO

3ai

100 MHzCDCl3

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

30

.9

40

35

.1

93

76

.6

81

77

.0

00

77

.3

17

10

9.

43

3

11

8.

63

31

21

.8

13

12

9.

55

6

13

4.

88

6

15

6.

51

8

I

tBu tBu

TfO

3ai

100 MHzCDCl3

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

7.37.47.57.67.77.8 ppm

7.

26

0

7.

32

4

7.

73

77

.7

39

3.

87

8

1.

87

1

2.22.42.6 ppm

2.

33

8

2.

55

6

5.

98

0

6.

00

0

I

TfO

3aj

400 MHzCDCl3

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

115120125130135140 ppm

11

6.

93

7

11

8.

74

5

12

1.

91

9

13

1.

84

7

13

4.

15

1

13

6.

78

01

37

.9

99

14

0.

34

8I

TfO

3aj

100 MHzCDCl3

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

7.07.17.2 ppm

7.

04

04

.0

00

2.22.42.62.8 ppm

2.

31

9

2.

50

1

6.

06

4

12

.1

05

I

TfO

3ak

400 MHzCDCl3

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

120125130135140145 ppm

11

7.

21

71

18

.8

42

12

2.

02

2

13

0.

90

2

14

2.

18

21

43

.8

00

18202224262830 ppm

20

.8

62

26

.0

53

I

TfO

3ak

100 MHzCDCl3

Al0,

t-.

-/6gr B----94!_ I

--BTT ' z

l ^e > H5 R =

V O

N l^ l\ J I

i l l

ICO aT

v l

I

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=:('o l

LL I IO - C D _

t lt l

E r e E ' z& E ? e ' z

qN

qr\

ogF*

q@

c\o

qco

qo Z O L '

qo,

olo,

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L 6 0 ' 6 -