CHAPTER V

Poly (N-vinyl-2-pyrrolidone)-Cu(OAc)2: An Efficient and Reusable

Catalyst for Sulfimidation

Chapter V

187

CHAPTER V

Poly (N-vinyl-2-pyrrolidone)-Cu(OAc)2: An Efficient and Reusable Catalyst for

Sulfimidation

Introduction

The vast chemistry of sulfoxides and sulfonium ylides make them very useful

reagents in organic synthesis. These compounds are important synthetic intermediates for

the construction of various chemically and biologically significant molecules.1 Several

successful methods have been developed for the synthesis of these compounds.2 But

Sulfimides, the nitrogen analogues of sulfoxides although have been widely used as

important auxillaries for chiral ligands and structural units in pseudopeptides,3 are less

investigated due to scarcity of appropriate nitrogen sources, as opposed to oxidants that

are available in wide variety and forms.4

Thus there have been many excellent methods developed for oxidation in terms of

stereoselectivity, mildness of reaction conditions, atom-efficiency and ecological

benignity; however the number of nitrogen-atom-transfer reactions satisfying such terms

has been very limited.3

In view of this, development of efficient methods for selective imidation of

sulfides to sulfimides has been desired for many years. However, only a few of them

have been found to yield the desired products in high yields under mild conditions.

State of the Art

In 1983, Groves and Takahashi reported that irradiation of Mn(porphyrin)(azide)

complex gave a nitride-Mn species that underwent aziridination by treatment with

trifluoroacetic anhydride in the presence of olefins, via an N-trifluoroacetyl nitrenoid

Chapter V

188

species.5 Later, nitride-Mn(salen) complex was also reported to undergo aziridination

under similar conditions.

Mansuy et al.6 demonstrated for the first time that PhI=NTs could convert Fe and

Mn complexes into corresponding nitrenoid species for aziridination and allylic

amination reactions, depending on the olefin used (Scheme 1).

PhI=NTs + FeIII

(TPP)

Ph Ph

NTs

Ph Ph

+ PhI + FeIII(TPP)

H2O

TsNH2 + [PhI=O + FeIII (TPP)]

or [PhI + (TPP)Fev=O ]

Ph Ph

O

Ph Ph

+ PhI + FeIII(TPP) + TsNH2

37%

Scheme 1

Evans et al.7

reported enantioselective aziridination of olefins using

bis(oxazoline)-copper complexes (Scheme 2).

Scheme 2

Jacobsen and co-workers studied the mechanistic aspects of the aziridination

reaction using Cu(I) (diimine) catalyst.8

Chapter V

189

Later, Bolm and co-workers3i

reported Fe(acac)3 catalyzed imidation of sulfides

and sulfoxides (Scheme 3).

Scheme 3

Latour and co-workers9 have reported amidation of thioanisole using a non-heme

iron complex (Scheme 4).

NFe

OFe

N

N

N

N

SH

III II

O O O O

X X

NFe

OFe

N

N

N

N

NHTs

III II

O O O O

X X

CH3CN

ArI=NTs

Scheme 4

Sharpless and co-workers10

reported metal free reactions in presence of

chloramine-T with moderate yields and longer reaction times (Scheme 5).

Scheme 5

Chapter V

190

Later, Bolm and co-workers11

described sulfimidation using 4-

nitobenzenesulfonamide (NsNH2) and iodobenzene diacetate [PhI(OAc)2] (Scheme 6).

Scheme 6

Initially, sulfimides were prepared in its chiral form either by conversion from

enantiomerically pure sulfoxides12

or by kinetic resolution of racemic sulfimides in the

presence of an optically active base.13

Later, Catalytic asymmetric sulfimidation using

PhI=NTs as nitrene donor in the presence of chiral Cu(I) bis(oxazoline) complex has

been described by Uemura et al.14

with moderate enantioselectivity albeit longer reaction

time (Scheme 7).

Scheme 7

Katsuki et al. reported asymmetric sulfimidation with good enantioselectivity

using Mn(salen)15

and Ru(salen)16

complexes (Scheme 8).

Chapter V

191

MePhS

MePhS+

-NTs

PhPh

O OMn

NMO (50mol%)

PhI=NTs, PhCl, rt

PF6

R

R

3'3

55%84%ee

Scheme 8

Owing to several economic and environmental advantages of heterogeneous

catalysts, like easy separation of the products reusability of the catalysts, heterogeneous

catalytic reactions are one of the most important ones and widely used in the industry.

Various supports have been used over the years to immobilize metal catalysts, one of the

important group among them are the polymers.

Polymer supported catalysts have been of great interest due to several advantages

such as the ease of product separation, isolation and reuse of the catalyst.17

But the use of

insoluble polymers as supports have some drawbacks as the reactivity and selectivity of

the supported catalysts is lesser than the unsupported analogs.18

Chapter V

192

In recent years, there have been intense efforts to develop methods to recover and

reuse homogenous catalysts.18,19

Poly (vinylpyrrolidone) (PVP) (Figure 1) is a water

soluble, biocompatible, physiologically inert polyamide polymer exhibiting unusual

colloidal and complexing properties.20

N

O

CH2

H2C

n

Figure 1. Molecular structure of PVP

PVP stabilized nanoscale metal colloids have been reported for selective

hydrogenation reactions21

(Scheme 9)

CH=CH C=O

H

CH=CH CH2OH

CH2 CH2 C=O

H

CH2 CH2 CH2OHPVP-metal nano-colloids

(1)

(2)

(3)

(4)

Scheme 9

Hu et al.22

reported PVP-CuCl2 catalyst for the oxidative carbonylation of

methanol to dimethyl carbonate (Scheme 10).

NO

Cu

ClCl

MeOH140oC; 1-7h;

Dimethyl carbonate

Scheme 10

Wang and co-workers23

reported PVP supported nanosized palladium metal

colloids for Sonogashira and Suzuki coupling reactions (Schemes 11 and 12).

Chapter V

193

H + I

Pd colloids on PVP

K2CO3, EtOH

Scheme 11

BF3K + X

R'R

Pd/PVP, K2CO3

H2O

R, R'= substituent

Scheme 12

Recently, Kantam et al.24

have reported catalytic sulfimidation of various sulfides

by using microencapsulated Cu(acac)2 and Cu(acac)2 immobilized in ionic liquids using

PhI=NTs (Scheme 13).

R2R1 S+

R2R1 S TsN=IPh

-NTs

MC-Cu(acac)2

R2R1 S+

R2R1 S TsN=IPh

-NTs

Cu(acac)2/ [bmim][BF4]

up to 92%

up to 94%

Scheme 13

There is a need for the development of new and efficient catalyst for the imidation

of sulfides with high selectivity, high atom efficiency and reusability.

Present Work

In this chapter, an efficient sulfimidation reaction using poly(vinylpyrrolidone)

supported cupric acetate in the presence of PhI=NTs [(N-(p-

tolylsulfonyl)imino]phenyliodinane) as nitrene donor has been described.

Scheme 14

Chapter V

194

Results and Discussion

Synthesis and Characterization of PVP-Cu(OAc)2

The preparation of PVP-Cu(OAc)2 was based on the literature procedure.22

Cupric

acetate (0.150 g) was added to a solution of PVP (Mw 40,000, 1g) in methanol (50 mL)

and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting solution

was concentrated under reduced pressure to give powdered PVP-Cu(OAc)2 (Cu 0.467

mmol/g). The copper content in the catalyst was found to be 2.93% by AAS analysis.

The resulting catalyst was characterized by powdered X-ray photoelectron spectroscopy

(XPS), TGA-MS, Electron spin resonance spectroscopy, UV-Vis Diffuse Reflectance

Spectroscopy (UV-DRS) and FTIR spectroscopic techniques.

FTIR spectroscopy

The FTIR analysis of PVP, fresh and used PVP-Cu(OAc)2 has been carried out

and the IR spectrum (Figure 1) of PVP showed a characteristic stretching band

corresponding to amide carbonyl group at 1657 cm-1

whereas in PVP-Cu(OAc)2, there is

a red shift of the amide carbonyl group to 1631 cm-1

with a shoulder at 1637 cm-1

indicating the interaction of the metal ion with amide carbonyl moiety of PVP.22

Both

PVP and PVP-Cu(OAc)2 showed characteristic bands at 2925 and 3418 cm-1

originating

from the amide group of PVP.

Chapter V

195

Figure 2. IR spectra of (a) PVP, (b) fresh catalyst and (c) used catalyst.

Chapter V

196

X-ray photoelectron spectroscopy (XPS)

The XPS survey scan of PVP-Cu(OAc)2 showed the presence of oxygen (535

eV), nitrogen (400 eV), carbon (285 eV) and copper (935 eV). High resolution narrow

scan for Cu 2p in PVP-Cu(OAc)2 catalyst showed binding energy peaks at 934.9 and

955.1 eV (Table 1) corresponding to Cu 2p3/2 and Cu 2p1/2 photoelectron transitions

respectively characteristic of Cu in +2 oxidation state. The observed binding energies

peaks of N 1s (398.9 eV) and O 1s (531.2 eV) in PVP-Cu(OAc)2 are close to N 1s (399.0

eV) and O 1s (531.8 eV) peaks in PVP. These results indicate the electronic modification

of Cu(II) on coordination with the amide moiety of PVP and thus, Cu(II) being

immobilized on the polymer. However, XPS spectrum of the used catalyst showed the

presence of both Cu(I) and Cu(II) states (Fig. 3b).

Table 1. XPS data for the binding energies (eV) of PVP, PVP- Cu(OAc)2 and used PVP-

Cu(OAc)2

XPS peak PVP PVP-Cu(OAc)2 Used PVP-Cu(OAc)2

N1s 399.0 398.9 398.6

O1s 531.8 531.2 531.2

Cu 2p3/2, 2p1/2 - 934.9, 955.1 (934.6, 955.6), (932.4, 952.0)a

[a] Binding energy of Cu in +1 oxidation state

Chapter V

197

Figure 3. XPS high resolution narrow scan of Cu 2p in (a) PVP-Cu(OAc)2 fresh catalyst

and (b) PVP-Cu(OAc)2 used catalyst

ESR and UV DRS spectroscopy

ESR and UV-Vis-DR spectroscopy have been used to understand the coordination

of Cu2+

ions in PVP. Both the fresh and used catalysts exhibit axial ESR spectra of Cu2+

ions at room temperature with resolved hyperfine structure (Fig. 5). The observed

hyperfine splitting parameters for the fresh and used catalyst are g = 2.38, 2.37; g⊥ =

2.08, 2.07, and A = 14, 13 mT respectively. The UV-Vis-DRS spectra (Fig. 6) showed

Chapter V

198

a characteristic absorption band at 700-750 nm corresponding to d-d transitions between

T2g and Eg terms typical for isolated Cu(II) ions in an octahedral environment with slight

tetragonal distortion. Another peak is observed around 300 cm-1

which can be ascribed to

the n-π* transition of the carbonyl group in PVP. The shoulder around 350 cm-1

is due to

the presence of the carbonyl group in the copper acetate. These results are in good

agreement with the ESR and UV-Vis DR spectra of Cu2+

ions in various zeolites.25

Figure 4. ESR spectra of Cu2+

ions in (a) fresh and (b) used PVP-Cu(OAc)2 catalyst at

the X-band recorded at room temperature.

Chapter V

199

Fig. 5. UV-Vis-DR spectrum of (a) fresh PVP-Cu(OAc)2 (b) Cu(OAc)2 (c) used PVP-

Cu(OAc)2 and (d) PVP.

Catalytic activity of PVP-Cu(OAc)2 in sulfimidation reaction

In the preliminary experiments, sulfimidation of thioanisole using PhI=NTs in the

presence of PVP-Cu(OAc)2 has been studied in various solvents under nitrogen

atmosphere (Table 2). The reaction was found to be more efficient in acetonitrile

compared to methanol, ethanol and 2-propanol and there was no reaction in DMF,

DMSO and water.

Chapter V

200

Table 2. Effect of solvents for the sulfimidation of thioanisole with PhI=NTs using PVP-

Cu(OAc)2a

Entry Solvent Yield (%)

1 Acetonitrile 98

2 Methanol 48

3 Ethanol 50

4 2-Propanol 50

5 DMF -

6 DMSO -

7 H2O -

[a] Reaction conditions: Thioanisole (0.5 mmole), PhI=NTs (0.5 mmol),

catalyst (0.025 g, 2.3 mol %), solvent (3 mL) under nitrogen atmosphere

for 0.6 h

Different nitrene donors were evaluated for the synthesis of sulfimides and the

results are shown in (Table 3). PhI=NTs was found to be more efficient nitrene donor

compared to chloramine-T and bromamine-T.

Table 3. Sulfimidation of thioanisole using different nitrene donors.

Nitrene donor Time (h) Yield (%)a

PhI=NTs

Chloramine-T

Bromamine-T

0.6

12

12

98

15

18

[a] Isolated Yields

Different sulfides were studied for the reaction under the optimized conditions using

PVP-Cu(OAc)2 as catalyst and the corresponding sulfimides were obtained in good to

excellent yields (Table 4). However, the reaction in the presence of Cu(OAc)2. H2O gave

Chapter V

201

the product in 50% yield (Table 4, entry 1). Aliphatic as well as aromatic sulfides were

equally effective for the reaction. Aromatic sulfides with electron-releasing substituents

were found to be more reactive than aromatic sulfides with electron-withdrawing

substituents (Table 4, entries 2 and 3). Whereas, sterically hindered sulfides, diphenyl

sulfide required longer reaction time (Table 4, entry 5).

Further, when the reaction was applied to allylic sulfides, there was no aziridination of

the double bond. Instead, [2,3] sigmatropic rearrangement with the formation of

sulfonamide through a sulfimide intermediate has been observed. Allylic sulfides were

less reactive and required longer reaction times when compared to aliphatic sulfides

(Table 4 entries 8 and 9). The catalyst was reused for several cycles and showed

consistent activity (Table 4, entry 1). The leaching of the metal after the fourth cycle was

determined by AAS analysis and was found to be 2 %.

Chapter V

202

Table 4. Sulfimidation of sulfides with PhI=NTs using PVP-Cu(OAc)2 a

Entry

1

2

3

4

Sulfide Time (min) Product Yield (%)

5

6

7

S

S

S

S

S

Br

S

S

8

9

S

NTs

S

NTs

S

NTs

Br

S

NTs

S

NTs

S3 3

S3 3

NTs

ClS

Cl S

NTs

SN

Ts

SN

Ts

40

35

40

120

210

30

40

50

180

98, 95b, 48c

98

82

96

75

98

90

78d

72d

-

-

-

-

-

+

+

+

+

+

+

+

-

-

[a]

Reaction condition: Sulfide (0.5 mmole), PhI=NTs (0.5 mmol), catalyst

(0.025 g, 2.3 mol %), acetonitrile (3 mL) under nitrogen atmosphere for 0.5 to

3.5 h.

[b] Yield after 4

th cycle.

[c]

In the presence of Cu(OAc)2.H2O (2.3 mol %). d[2,3] sigmatropic

rearrangement.

Chapter V

203

In order to extend the scope of this methodology, the asymmetric synthesis of

sulfimides using 4, 4’-disubstituted bis(oxazolines) 1a and 1b (BOX) as chiral ligands

was carried out under similar reaction conditions (Scheme 15). When bis(oxazoline)

ligand 1a was used, higher ees were obtained in comparison to the reaction with 1b as the

ligand. Sulfides with electron donating substituents gave higher ee’s when compared to

the sulfides with electron withdrawing substituents (Table 5).

BOX (3-5 mol%) upto 68% ee

SR R'

PVP-Cu(OAc)2;CH3CN

PhI=NTs, rt RS

R'

NTs-

+ *

O

N N

O

R R

1a R = t- butyl 1b R = Ph

BOX

Scheme 15

Chapter V

204

Table 5. Asymmetric sulfimidation of sulfides with PhI=NTs using PVP-Cu(OAc)2 .a

Entry Substrate Ligand Isolated yield% % eeb[a]

1

SCH3

SCH3

SCH3

Br

2

3

1a

1b

1a

1b

1a

1b

95

96

95

95

78

80

50

10

7

4

68

5

92 24c

5Cl

S

4

S 1a

1b

1a

1b

90

80

88

85

5

2

60

5

Time (min)

35

40

40

120

40

[a]

Reaction condition: Sulfide (0.5 mmol), PhI=NTs (0.5 mmol), catalyst (0.025g,

2.3 mol%), bis(oxazoline)/Cu = 2, acetonitrile (3 mL) were used.

[b] The ee values were determined by HPLC using Daicel Chiralcel OJ-H column

(hexane/2-propanol = 4 : 1, flow rate 1.0 mL/min).

[c] With bis(oxazoline)/Cu = 1.

Reusability study of the catalyst in asymmetric sulfimidation

The catalyst was recovered, reused and the results are summarized in Table 6. The

decrease in enantioselectivity in the recycle experiments can be explained by the TGA-

MS studies of the bis(oxazoline) ligand in the fresh and the used catalyst.

Chapter V

205

Table 6. Recovery and reuse of PVP-Cu(OAc)2-BOX catalyst for asymmetric

sulfimidation of thioanisole.a

Entry Cycle no Isolated yield (%) ee%b

1 1 95 50

2 2 95 15, 50c

3 3 95 15

[a] Reaction condition:Sulfide (0.5 mmol), PhI=NTs (0.5 mmol), catalyst (0.025g)

acetonitrile (3 mL) were used.

[b] 2

nd and 3

rd cycle ee% obtained without the use of additional amount of ligand

[c] 3 mol% of ligand added.

As can be seen in Fig. 6 and 7, the evolved gas fragments as a function of

temperature showed the fragments m/Z values 15, 57, 84 and 126 a.m.u in both the

catalysts resulting from the presence of tertiary butyl substituted bis(oxazoline) ligand in

the catalyst. Remarkable changes were observed in the onset of the decomposition

temperatures in both the fresh and used catalyst. In the fresh catalyst the onset of the

ligand decomposition is observed at 425 oC whereas in the recovered catalyst it is

observed at 250 o

C, at much lower temperature. This clearly suggests that in the fresh

catalyst, the ligand is chemisorbed where as in the recovered catalyst the ligand appears

to be physically adsorbed, so the decrease in the onset of decomposition. These ligand

molecules present on the surface of the support are responsible for the 15% ee’s in the

recycle experiments, however consistent yield of the product was obtained in all the

recycles. On the other hand, addition of fresh amounts of ligand after the first cycle gave

the product with 50 % ee. Therefore, it can be concluded that the immobilization of

Chapter V

206

bis(oxazoline) ligand-Cu complex by electrostatic interactions cannot be properly

performed due to its low binding constant leading to the presence of ligand free copper

on the support after the first cycle, which noticeably reduces the enantioselectivity.

Fig. 6. TGA-MS of the fresh catalyst with t-butyl bis(oxazoline) ligand.

Chapter V

207

Fig 7. TGA-MS of the used catalyst with t-butyl bis(oxazoline) ligand.

Plausible Mechanism

A plausible mechanism of the sulfimidation reaction can be proposed on the basis

of the literature reports.16a

First the metal nitreneoid species (2) is formed by the

interaction of PhI=NTs with the catalyst by the loss of the labile acetate ligand (L), then

the intermediate sulfide-metal nitrene species (3) is formed in the next step by the

interaction of the metal with the sulfide, this sulfide-metal-nitrene species subsequently

losses the iodobenzene molecule and forms the S-N bond (4). This intermediate having

sulfide moiety bonded directly to the nitrene species then forms the sulfimide product.

The redox process involving Cu(II) and Cu(I) takes place during the course of the

reaction which is detected by XPS analysis of the new catalyst and the used catalyst

(Scheme 16).

Chapter V

208

N

Ts

S

R'

R

Cu

L

L

Cu

L

N

IPhTs

- L

PhI=NTs

RS

R'

PhI

Cu

N

Ts

Cu

RS+

R'

-NTs

II

II

II

II

= PVP

L= Acetate+2L

- L

RS

R'

PhI

Cu

I

(1)

(2)

(3)

(4)(5)

Scheme 16

Conclusions

In summary, PVP-Cu(OAc)2 was synthesized, well characterized and employed as a

catalyst for the sulfimidation of sulfides in the presence of PhI=NTs ([N-(p-

tolylsulphonyl)imino]-phenyliodinane) as nitrene donor to afford the corresponding

sulfimides in good to excellent yields. In the presence of chiral bis(oxazoline) ligand,

asymmetric induction occurs to afford chiral sulfimides with moderate

enantioselectivities. The catalyst can be reused for several cycles with consistent activity.

Chapter V

209

Experimental Section

General

X-ray photoelectron spectra were recorded on a KRATOS AXIS 165 with a dual

anode (Mg and Al) apparatus using the Mg-Kα anode. The pressure in the spectrometer

was about 10-9

Torr. For energy calibration the carbon 1s photoelectron line is used. The

carbon 1s binding energy was taken to be 285.0 eV. The spectra were deconvoluted using

Sun Solaris based Vision 2 curve resolver. The location and the full width at half

maximum (FWHM) for a species was first determined using the spectrum of a pure

sample. The location and FWHM of products which were not obtained as pure species

were adjusted until the best fit was obtained. Symmetric Gaussian shapes were used in all

cases. Binding energies for identical samples were in general, reproducible to within ±

0.1 eV. Diffuse reflectance UV-Vis absorption spectra for samples as KBr pellets were

recorded on a GBC Cintra 10e in the range 200-800 nm with a scan speed of 400 nm/min.

ESR spectra were recorded on JEOL JES-FA 200 ESR spectrometer operating in the X-

band frequencies with a field modulation of 100 kHz. The microwave frequency was set

at 9.45 GHz and the magnetic field was scanned between 225 mT to 425 mT. Infrared

spectra were recorded on a Thermo Nicolet Nexus 670 FT-IR spectrometer as KBr

pellets. Thermogravimetric (TG), differential thermal analysis (DTA) and mass of the

evolved gas during the thermal decomposition of the catalyst were studied on

TGA/SDTA Mettler Toledo 851e system coupled to MS Balzers GSD 300T, using open

alumina crucibles, containing samples weighing about 8-10mg with a linear heating rate

of 10oC min

-1. NMR spectra were recorded on a Varian Gemini (200 MHz), Bruker

Avance (300 MHz), Varian Unity (400MHz) spectrometer using TMS as an internal

Chapter V

210

standard and CDCl3 as solvent. Mass spectra were obtained at an ionisation potential of

70 eV [scanned on VG 70-70H (micro mass)]. Only selected ions are presented here.

Melting points were recorded on Barnstead electrothermal 9200 instrument and are

uncorrected. CHNS analysis was performed on a Vario EL analyzer. High performance

Liquid Chromatography (HPLC) was performed using AGILENT-1100 series liquid

chromatograph equipped with a single pump and UV detector (fixed at 205 nm) using

CHIRACEL-OJ-H capillary column with isopropanol/hexane as eluting agent. All the

other solvents and chemicals were obtained from commercial sources and purified using

standard methods. PVP (K=30) was purchased from Fluka. Cu(OAc)2. H2O was

purchased from S.D Fine Chemicals, India. Iodobenzene diacetate, p-toluene sulfonamide

and sulfides were purchased from Aldrich or Fluka and used without further purification.

ACME silica gel (100–200 mesh) was used for column chromatography. Thin-layer

chromatography was performed on Merck-precoated silica gel 60-F254 plates. All the

other solvents and chemicals were obtained from commercial sources and purified using

standard methods.

Synthesis of PVP-Cu(OAc)2 catalyst

The preparation of PVP-Cu(OAc)2 was based on the literature procedure.22

Cupric acetate (0.150 g) was added to a solution of PVP (Mw 40,000, 1g) in methanol

(50 mL) and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting

solution was concentrated under reduced pressure to give powdered PVP-Cu(OAc)2 (Cu

0.467 mmol/g). The copper content in the catalyst was found to be 2.93% by AAS

analysis.

Chapter V

211

Typical procedure for sulfimidation using PVP-Cu(OAc)2

To acetonitrile (3 mL) were added PVP-Cu(OAc)2 (0.025 g, 2.3 mol %), methyl phenyl

sulfide (0.062 g, 0.5 mmol) and PhI=NTs (0.186 g, 0.5 mmol) and the reaction mixture

was stirred at room temperature for the appropriate time as shown in Table 2. The

reaction was monitored by the disappearance of PhI=NTs from the reaction mixture and

by thin layer chromatography. After completion of reaction, the reaction mixture was

concentrated and washed with 1:4 hexane/ethyl acetate. The combined organic extracts

were concentrated and the crude solid was purified by recrystallization from iso-propanol

and water or by column chromatography on silica gel (hexane/ethyl acetate, 20/80 v/v as

eluent) to afford the pure product as white solid.

Representative examples

S-p-tolyl, S-methyl N-p-toluenesulfonyl sulfimide (Table 4, entry 2)

Figure 8. 1H NMR (CDCl3, 300 MHz): δ = 2.37 (s, 3H), 2.43 (s, 3H), 2.82 (s, 3H), 7.15

(d, 2H), 7.29 (d, J= 8.3 Hz, 2H), 7.59 (d, J= 8.3 Hz, 2H), 7.71 (d, J= 8.3 Hz, 2H).

Figure 9. 13

C NMR (CDCl3, 75 MHz): δ = 21.35, 21.40, 39.15, 43.38, 123.5, 125.82,

126.25, 129.12, 130.00, 129.08, 130.60, 132.72, 141.29, 141.29, 141.57, 143.32.

S-Phenyl, S-ethyl, N-p-toluenesulfonyl sulfimide (Table 4, entry 4)

Figure 10. 1H NMR (CDCl3, 300 MHz): δ = 1.21 (t, J= 6.7 Hz, 3H), 2.36 (s, 3H), 3.00

(q, J= 6.7, 12.8 Hz, 2H), 7.15 (d, J= 8.3 Hz, 2H), 7.50 (d, 2H, Ar-H), 7.70 (m, 5H).

Figure 11. 13

C NMR (CDCl3, 75 MHz): δ = 21.33, 47.82, 126.22 (2C), 126.25 (2C),

129.08 (2C), 129.77 (2C), 132.26 (2C), 141.30, 141.53.

Rest of the products were characterized similarly and the results obtained were

similar to that reported in the literature.14, 16, 26

Chapter V

212

References

1. (a) J. Drabowski, P. Kielbasinski, M. Mikolajezyk, Synthesis of Sulfoxides, Wiley,

New York, 1994; (b) M. Mikolajczyk, Tetrahedron 1986, 42, 549.

2. (a) T. L. Gilchrist, C. J. Moody, Chem. Rev. 1977, 77, 409; (b) E. G. Mata

Phosphorus, Sulfur Silicon Related Elem. 1996, 117, 231; (c) H. Kagan, T.

Luukas Transition Met. Org. Synth. 1998, 2, 361.

3. (a) C. Bolm, K. Muniz, J. P. Hildebrande, Comprehensive Asymmetric Catalysis

Ed. E. N. Jacobsen, A. Pfaltz, H. Yamamoto, Berlin: Springer 1999, 697; (b) H.

B. Kagan, Catalytic Asymmetric Synthesis, Ed. I. Ojima, New York: Wiley-VCH

2000, 327; (c) I. Fernandez, N. Khiar, Chem. Rev. 2003, 103, 3651; (d) K. Hiroi,

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