S1  

Supplementary Information Intermolecular Sulfenoamination of Alkenes with Sulfonylamides

and N-Sulfanylsuccinimides for the Synthesis of -Sulfonylamino

sulfides and Dihydrobenzothiazines

Tao Liu,a Jun Tian,b Wen-Chao Gao,*a Hong-Hong Chang,a Qiang Liu,*a Xing Li,a

and Wen-Long Weia

a College of Chemistry and Chemical Engineering, and b College of Data Science,

Taiyuan University of Technology, Taiyuan 030024, P. R. China

E-mail: gaowenchao@tyut.edu.cn

        liuqiang@tyut.edu.cn

Table of contents

Table S1. Optimization of reaction conditions for the synthesis of 11a.....S2

MS on Mechanism Study..........................................................................S3

Ring Opening of Phenyl N-tosylaziridine with Thiocresol......................S5

Crystal Structure of 4m and the Corresponding Data..............................S5

Crystal Structure of 9 and the Corresponding Data.................................S6

NMR Spectra of Products........................................................................S8

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017

S2  

Table S1. Optimization of reaction conditions for the synthesis of 11aa

a Reaction conditions: 1a (0.2 mmol), 2e (0.3 mmol), and 3a (0.22 mmol) was subjected to the

indicated conditions. b Isolated yield.

Entry Conditions Yield (%)b

1 1) TfOH (20 mol %), CH2Cl2 (1 mL), 60 oC;

2) Pd(OAc)2 (20 mol %), BINAP (40 mol %), K2CO3 (2.5 eq), Toluene, 110 oC

0

2 1) TfOH (20 mol %), Toluene (1 mL), 60 oC;

2) Pd(OAc)2 (20 mol %), BINAP (40 mol %), K2CO3 (2.5 eq), Toluene, 110 oC

0

3 1) TfOH (20 mol %), CH2Cl2 (1 mL), 60 oC;

2) CuI (10 mol %), ethylenediamine (20 mol %), K2CO3 (2.0 eq), 1,4-Dioxane, 100 oC

0

4 1) TfOH (20 mol %), CH2Cl2 (1 mL), 60 oC;

2) Cu (1.1 eq), DMF (1 mL), N2, 120 oC

27

5 1) TfOH (20 mol %), DCE (1 mL), 60 oC;

2) Cu (1.1 eq), DMF (1 mL), N2, 120 oC

0

6 1) TfOH (20 mol %), Toluene (1 mL), 60 oC;

2) Cu (1.1 eq), DMF (1 mL), N2, 120 oC

66

7 1) TfOH (20 mol %), Toluene (0.5 mL), 60 oC;

2) Cu (1.1 eq), DMF (1 mL), N2, 120 oC

72

8 1) BF3·Et2O (20 mol %), Toluene (1 mL), 60 oC;

2) Cu (1.1 eq), DMF (1 mL), N2, 120 oC

54

S3  

MS on Mechanism Study

Mass spectroscopy (MALDI) for the reaction of 1a with 2a

 

 

S4  

Mass spectroscopy (MALDI) for the reaction of 1j with 2a 

Ph Ph

O BF3Et2O (20 mol%)

Ph

PhO

SMe

Chemical Formula: C22H19OS+

Exact Mass: 331.12

CH2Cl2, rt

10-20 min

N

O

O

S

Me

+

1j 2a 

S5  

Synthesis of -Sulfonamino Sulfides through Ring Opening of Phenyl

N-tosylaziridine with p-Thiocresol

Ph

STol

NHTs

Ph

N

Ts

Ph

NHTs

STol +K2CO3 (1.1 equiv)p-Thiocresol (1.1 equiv)

toluene, reflux, 6 h

yield : 90%ratio = 1: 1.25

10 4a 4a'

Crystal Structure of 4m and the Corresponding Data 

ORTEP drawing of 4m (CCDC 1528230); thermal ellipsoids are set at a 30%

probability level

Crystal Structure Information of 4m

Crystal data

Chemical formula C29H27ClNO3S2

Mr 537.08

Crystal system, space group Monoclinic, P21/c

Temperature (K) 290

a, b, c (Å) 10.7451 (4), 24.1196 (8), 10.5407 (4)

β (°) 100.488 (1)

V (Å3) 2686.17 (17)

Z 4

Radiation type Mo Kα

S6  

µ (mm−1) 0.33

Crystal size (mm) 0.25 × 0.20 × 0.10

Data collection

Diffractometer Bruker APEX-II CCD diffractometer

Absorption correction Multi-scan SADABS

No. of measured, independent and observed [I > 2σ(I)] reflections

25814, 6640, 4696

Rint 0.038

(sin θ/λ)max (Å−1) 0.667

Refinement

R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.157, 1.06

No. of reflections 6640

No. of parameters 327

H-atom treatment H-atom parameters constrained

Δρmax, Δρmin (e Å−3) 0.32, −0.51

Crystal Structure of 9 and the Corresponding Data 

ORTEP drawing of 9 (CCDC 1528231); thermal ellipsoids are set at a 30%

probability level

S7  

Crystal Structure Information of 9

Crystal data

Chemical formula C19H23NO2S2

Mr 361.50

Crystal system, space group Monoclinic, P21/c

Temperature (K) 284

a, b, c (Å) 10.7682 (5), 18.6312 (8), 10.2412 (5)

β (°) 110.113 (1)

V (Å3) 1929.34 (15)

Z 4

Radiation type Mo Kα

µ (mm−1) 0.29

Crystal size (mm) 0.30 × 0.25 × 0.18

Data collection

Diffractometer Bruker APEX-II CCD diffractometer

Absorption correction Multi-scan SADABS

No. of measured, independent and observed [I > 2σ(I)] reflections

18068, 4730, 3414

Rint 0.031

(sin θ/λ)max (Å−1) 0.666

Refinement

R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.163, 1.01

No. of reflections 4730

No. of parameters 219

H-atom treatment H-atom parameters constrained

Δρmax, Δρmin (e Å−3) 0.50, −0.42

S8  

NMR Spectra of Products 

 

4a

S9  

 

4a

S10  

 

 

4b

S11  

 

4b

S12  

 

 

4c

S13  

 

4c

S14  

 

 

4d

S15  

 

 

4d

S16  

 

 

4e

S17  

 

 

4e

S18  

 

 

4f

S19  

 

 

4f

S20  

 

 

4g

S21  

 

 

4g

S22  

 

 

4h

S23  

 

 

4h

S24  

 

4i

S25  

 

4i

S26  

 

 

4j

S27  

 

 

4j

S28  

 

 

4k

S29  

 

 

4k

S30  

 

 

4l

S31  

 

 

4l

S32  

 

 

4m

S33  

 

 

4m

S34  

 

 

4n

S35  

 

 

4n

S36  

 

4o

S37  

 

4o

S38  

 

 

4pa+4pb

S39  

 

 

4pa

S40  

 

 

4pa

S41  

 

 

4q

S42  

 

 

4q

S43  

 

 

4r

S44  

 

 

4r

S45  

 

 

4s

S46  

 

 

4s

S47  

 

 

4s

S48  

 

 

8

S49  

 

 

8

S50  

 

 

9

S51  

 

 

9

S52  

 

 

4t

S53  

 

 

4t

S54  

 

 

4u

S55  

 

 

4u

S56  

 

 

4v

S57  

 

 

4v

S58  

 

 

4w

S59  

 

 

4w

S60  

 

 

4x

S61  

 

 

4x

S62  

 

 

4y

S63  

 

 

4y

S64  

 

 

4z

S65  

 

 

4z

S66  

 

 

4aa

S67  

 

 

4aa

S68  

 

 

4bb

S69  

 

4bb

S70  

 

S71  

 

11a

S72  

  

11a

S73  

 

11b

S74  

 

 

11b

S75  

 

11c

S76  

 

11c

S77  

 

11d

S78  

 

11d

S79  

 

11e

S80  

 

11e

S81  

 

11f

S82  

 

 

11f

S83  

 

11g

S84  

 

 

11g

S85  

 

13

S86  

 

13

S87  

 

14

S88  

 

 

14