Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent [2,3]-Sigmatropic Rearrangement

中文 / Bilingual · English version

${}^{a}$ Department of Chemistry, Tongji University, Shanghai 200092, China ${}^{b}$ Faculty of Science, Kunming University of Science and Technology, Kunming, Yunnan 650093, China ${}^{c}$ Beijing National Laboratory of Molecular Sciences (BNLMS) and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China

A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and subsequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within ${10}\mathrm{\;{min}}$ , providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.

Keywords allyl sulfonamide, allyl sulfide, transition-metal-free reaction, sigmatropic rearrangement, nitrene

Introduction

The construction of carbon-nitrogen bond is one of the major topics in organic synthesis as the nitrogen is ubiquitous in natural products and biologically active agents. Similar to the related carbene species, nitrene is highly reactive species and can undergo various transformations, such as C-H bond insertions and aziridina-tions. ${}^{\left\lbrack 1\right\rbrack }$ These reactions can serve as useful approaches toward carbon-nitrogen bond formation. The reaction of nitrene with sulfides affords sulfilimines, which have diverse reactivities. ${}^{\left\lbrack 2\right\rbrack }$ When allylsulfides are employed in this reaction, the corresponding sulfilimines bearing allylic substituent will undergo [2,3]-sigmatropic rearrangement to afford allylic amides. ${}^{\left\lbrack 3\right\rbrack }$ This unique transformation is considered as an interesting method for the synthesis of allylic amine derivatives.

Copper-catalyzed formation of sulfimides and se-lenimides and subsequent [2,3]-sigmatropic rearrangement to the corresponding allylic sulfonamides using [ $N$ -( $p$ -tolylsulfonyl)imino] phenyliodinane (TsN = IPh) as nitrogen source has been reported by Uemura and coworkers. ${}^{\left\lbrack 4\right\rbrack }$ The iron-catalyzed imidation of sulfides with tert-butoxycarbonyl azide and [2,3]-sigmatropic rearrangement has been investigated by ${\operatorname{Bach}}^{\left\lbrack 5\right\rbrack }$ and van Vranken ${}^{\left\lbrack 6\right\rbrack }$ respectively. Very recently, the synthesis of allenamides has been achieved by Armstrong ${}^{\left\lbrack 7\right\rbrack }$ through this rearrangement by employing CbzNHOTf as the nitrene precursor.

As the continuation of our own interest in [2,3]- sigmatropic rearrangement of sulfide ylides ${}^{\left\lbrack 8\right\rbrack }$ and transition-metal-free transformations, ${}^{\left\lbrack 9\right\rbrack }$ we have investigated the metal-free imidation of allyl sulfides 1 by using chloramine-T (TsNClNa) as the nitrogen source. ${}^{\left\lbrack 3\right\rbrack }$ The subsequent [2,3]-sigmatropic rearrangement affords allyl sulfonamides 2 in good yields (Scheme 1).

Scheme 1 Imidation/[2,3]-sigmatropic rearrangement

The products contains sulfonamide segment which serves as one of the common structural features in drugs. ${}^{\left\lbrack {10}\right\rbrack }$ Furthermore, they can also be converted to allyl sulfonamides and allyl amides by removal of the protecting group (Ts). ${}^{\left\lbrack 5,{11}\right\rbrack }$

Results and Discussion

The allyl sulfides were prepared and their reactions with chloramine-T were investigated. The allyl(phenyl)- sulfane 1a was selected to optimize the reaction conditions (Table 1). Initially, only trace of product could be detected when we conducted the reaction in toluene as the solvent under room temperature (Table 1, Eentry 1).

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Received June 20, 2012; accepted July 4, 2012.

Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200604 or from the author.

Dedicated to the 80th Anniversary of Chinese Chemical Society.

The yield was increased to 50% when we elevated the reaction temperature to ${70}{}^{ \circ }\mathrm{C}$ (Table 2, Eentry 1). We continued to tried other solvents and found that DCE, THF, DMF and dioxane could afford moderate yields (Table 2, Entries 3-6), while MeCN and EtOH afforded excellent yields (Table 2, Entries 7-12). Moderate yields can also be obtained when ${\mathrm{H}}_{2}\mathrm{O}$ was used as the solvent under heating or microwave conditions (Table 1, Entries 14-16). Notably, more favored yields can be achieved under room temperature other than 70 C when MeCN or EtOH was chosen as the medium (Table 1, Entries 10, 12).

Table 1 Optimization of the reaction conditions with 1a

${}^{a}$ Determined by TLC. ${}^{b}$ Isolated yields. ${}^{c}$ Yield using anhydrous chloramine-T was given in parentheses. ${}^{d}$ Amount of recovered staring material was not determined.

The optimized reaction conditions (EtOH/room temperature) were then applied to a series of allyl sulfides $\mathbf{1}\mathbf{b} - \mathbf{1}\mathbf{q}$ and the results were summarized in Table 2. All aromatic allyl sulfides reacted smoothly with chloramines-T and afforded excellent yields. The sub-stituents on the aromatic ring had some influences on the reaction. When electron-donating aromatic allyl sulfides were subjected to the reaction, the yields slightly increased (Table 2, Entries 1, 2, 4, 9), while the yields decreased when the aromatic ring bears electron-withdrawing group (Table 2, Entries 3, 5). Various substituted and cyclic allyl sulfides could also be used for the construction of C-N bonds (Table 2, Entries 6-9). The benzyl and alkyl allyl sulfides react slowly at room temperature, they could work successfully when heated to 70 °C (Table 2, Entries 10, 11). Moreover, functional groups such as bromine, hydroxyl, protected amido and aldehyde on allyl part are tolerant in this system (Table 2, Entries 12-16). It is worth noting that this reaction proceeds very fast and could complete within 10 min in all cases.

Conclusions

In summary, we have developed a process of metal-catalyst free imidation of allyl sulfides with Chlor-amines-T and subsequent [2,3]-sigmatropic rearrangement. Various substituted and functionalized allyl sul-fonamides or allyl amides can be easily obtained through this approach. It affords an efficient strategy for the construction of carbon-nitrogen bond. Compared to other procedures, this method has wider scope and higher efficiency.

Experimental

General

Aryl mercaptans, bromides and chloramine-T were purchased from Alfa Aesar. Chloroform-d and dimethylsulfoxide- ${d}_{6}$ were purchased from Cambridge Isotope Laboratories. All solvents were distilled prior to use. THF was freshly distilled from Na before use. All reactions were performed in air atmosphere. For chromatography, 200—300 mesh silica gel (Qingdao, China) was employed. ${}^{1}\mathrm{H}$ NMR (300 or ${200}\mathrm{{MHz}}$ ) and ${}^{13}\mathrm{C}$ NMR (75 or ${50}\mathrm{{MHz}}$ ) spectra were measured on Varian ${300}\mathrm{{MHz}}$ spectrometers; ${}^{1}\mathrm{H}$ NMR (400 MHz) and ${}^{13}\mathrm{C}$ NMR (100 MHz) spectra were measured on Bruker ARX 400 MHz spectrometer. ${\mathrm{{CDCl}}}_{3}$ was used as solvent with tetramethylsilane (TMS) as internal standard. IR spectra were recorded with a Nicolet 5MX-S infrared spectrometer.

Table 2 Reaction of $1\mathrm{\;b} - 1\mathrm{q}$ with chloramine-T under qptimization conditions

Entry	Allyl sulfide 1	Product 2	Yield ${}^{a}$ %
1	1b	2b	90
2	1c	2c	92

Continued

Entry	Allyl sulfide 1	Product 2	Yield ${}^{a}/\%$
3	1d		72
4	1e	2e	97
5	1f	2f	78
6	1g	2g	78
7	1h	2h	77
8	1i	2i	93
9	1j		95
${10}^{b}$	1k	2k	45
${11}^{b}$	11	21	91
12	1m	2m	84
13	1n	2n	83
${14}^{c}$			82
	10	20

Continued

Entry	Allyl sulfide 1	Product 2	Yield ${}^{a}/{}^{w}$
15	1p	2p	84
${16}^{b}$	1q	2q	68

${}^{a}$ Isolated yields. ${}^{b}$ The reaction was carried out at ${70}{}^{ \circ }\mathrm{C}{}^{c}$ d.r. $= {60} : {40}$ .

Synthesis and spectral data for the substrates 1a-1q and 3-4

(E)-Ethyl 4-(phenylthio)but-2-enoate (3): ${}^{\left\lbrack {12}\right\rbrack }$ A 2.05 mL portion of thiophenol (2.2 g, 20 mmol) and 5.13 g of (E)-ethyl 4-bromobut-2-enoate (22 mmol) were dissolved in ${30}\mathrm{\;{mL}}$ of dry diethyl ether and cooled to-10 °C. A ${2.2}\mathrm{\;g}$ portion of triethylamine $\left( {{22}\mathrm{{mmol}}}\right)$ was added dropwise during ${0.5}\mathrm{\;h}$ . After being stirred at $- {10}{}^{ \circ }\mathrm{C}$ for ${30}\mathrm{\;{min}}$ , the mixture was refluxed for $1\mathrm{\;h}$ and stirred overnight at room temperature. The precipitate was removed by filtration and washed with diethyl ether. The filtrate was washed with aqueous $\mathrm{{NaOH}}$ and dried over ${\mathrm{{MgSO}}}_{4}$ . After the solvent was removed the residue was purified by column chromatography. ${4.35}\mathrm{\;g}$ (98%) of 3 was obtained as a colorless liquid.

(E)-4-(Phenylthio)but-2-enal (4): ${}^{\left\lbrack {13}\right\rbrack }$ A ${0.72}\mathrm{\;g}$ (4 mmol) portion of $\left( E\right)$ -ethyl-4-(phenylthio)but-2-enoate (3), ${0.672}\mathrm{\;g}{\mathrm{{NaHCO}}}_{3}$ and ${2.035}\mathrm{\;g}$ of DMP were added to ${20}\mathrm{\;{mL}}$ of ${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}$ under $0{}^{ \circ }\mathrm{C}$ and the reaction was conducted by TLC. Flash chromatography provided crude product which was further purified by column chromatography providing ${0.584}\mathrm{\;g}\left( {{82}\% }\right) 4$ as a colorless liquid.

General procedure for the preparation of 1a- 1m: ${}^{\left\lbrack {14} - {19}\right\rbrack }$ To a ${15}\mathrm{\;{mL}}$ of dry THF was added ${12}\mathrm{\;{mmol}}$ of NaH, 10 mmol of thiol (slowly added) and stirred at 0 °C for 15 min. To the system was then added 12 mmol of allyl bromide and stirred overnight at room temperature. The precipitate was removed by filtration and washed with diethyl ether. After the solvent was removed the residue was purified by column chromatography.

(4-Chlorophenyl)(cyclohex-2-enyl)sulfane (1f): Colorless liquid; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.34}(\mathrm{\;d}$ , $J = {8.4}\mathrm{\;{Hz}},2\mathrm{H}),{7.25}\left( {\mathrm{\;d}, J = {8.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.85}(\mathrm{\;{dd}}, J =$ 3.50,9.9 Hz,1H),5.74 (dd, $J = {1.8},{10.0}\mathrm{\;{Hz}},1\mathrm{H}$ ),3.81 (s, br, 1H), 2.04-1.58 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {134.3},{132.6},{130.7},{128.9},{126.5},{44.2},{28.7}$ , 24.8, 19.3; IR (film) v: 2933, 1476, 1096, 1013, 815 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {224}\left( {11}\right) ,{143}$ (16), 108 (18), 81 (100), 53 (14); HRMS calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{13}\mathrm{{ClSK}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {263.0058}$ , found 263.0053.

Cyclohex-2-enyl(4-methoxyphenyl)sulfane (1j): Colorless liquid; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ :7.41 (d, $J = {8.7}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${6.84}\left( {\mathrm{\;d}, J = {8.62}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${5.81} - {5.73}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{3.79}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{3.65}\left( {\text{ br }\mathrm{s},1\mathrm{H}}\right)$ , 2.00-1.54 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta : {159.3},{135.1},{130.0},{127.2},{125.7},{114.3},{55.2},{45.4}$ , 28.7, 24.9, 19.4; IR (film) v: 2933, 1492, 1243, 1029, ${823}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {220}\left( {21}\right)$ , 140 (100),81 (55); HRMS calcd for ${\mathrm{C}}_{13}{\mathrm{H}}_{15}\mathrm{{OS}}{\left( \mathrm{M} - \mathrm{H}\right) }^{ + }$ : 219.0838, found 219.0838.

(E)-4-(Phenylthio)but-2-en-1-ol (1n): ${}^{\left\lbrack {20}\right\rbrack }$ A 0.666 g (3 mmol) portion of (E)-ethyl-4-(phenylthio) but-2- enoate (3) was dissolved in ${10}\mathrm{\;{mL}}$ of dry THF and cooled to 0°C. A 6 mL portion of Dibal-H (6 mmol, 1n in hexane) was added, and after the mixture was stirred at $0{}^{ \circ }\mathrm{C}$ for $1\mathrm{\;h},2\mathrm{\;{mL}}$ of methanol, ${10}\mathrm{\;{mL}}$ of water,1 $\mathrm{{mL}}$ of saturated $\mathrm{{NaOH}}$ aqueous, and ${10}\mathrm{\;{mL}}$ of aqueous KNa tartrate $\left( {{30}\% , W/W}\right)$ were added successively. The mixture was stirred at room temperature for $1\mathrm{\;h}$ , and the layers were separated. The aqueous layer was extracted with ${30}\mathrm{\;{mL}}{\mathrm{{Et}}}_{2}\mathrm{O}$ for three times, and the combined organic layers were washed with water and brine and dried over ${\mathrm{{MgSO}}}_{4}$ . After evaporation of the solvent, the residue was purified by column chromatography. Compound $1\mathrm{n}\left( {{0.443}\mathrm{\;g},{82}\% }\right)$ was obtained as a colorless liquid. ${}^{1}\mathrm{H}$ NMR (300 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.34} - {7.16}(\mathrm{\;m}$ , 5H), 5.75-5.70 (m, 2H), 4.04 (d, J=4.2 Hz, 2H), 3.54 $\left( {\mathrm{d}, J = {5.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.73}\left( {\mathrm{\;s},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}\mathrm{{NMR}}({75}\mathrm{{MHz}}$ , ${\mathrm{{CDCl}}}_{3}$ ) $\delta$ :135.6,132.3,129.8,128.7,126.8,126.2,62.7, 35.7.

(E)-1-Phenyl-4-(phenylthio)but-2-en-1-ol (1o): In a 25 mL round bottom flask a magnetic stir bar was placed and the apparatus was flame dried. Then, dried diethyl ether (10 mL), phenylmagnesium bromide (4.5 mmol,3 mol/L in diethyl ether) and 0.534 g (3 mmol) of $\left( E\right)$ -4-(phenylthio)-but-2-enal (4) were added to the flask under $0{}^{ \circ }\mathrm{C}$ . After stirred at room temperature for ${30}\mathrm{\;{min}}$ , the reaction was quenched by slow addition of a saturated ${\mathrm{{NH}}}_{4}\mathrm{{Cl}}$ solution followed by extraction with diethyl ether $\left( {{15}\mathrm{\;{mL}} \times 3}\right)$ . The combined organic layers were washed with brine, dried $\left( {{\mathrm{{Na}}}_{2}{\mathrm{{SO}}}_{4}}\right)$ , concentrated and the crude product was purified by column chromatography to afford ${0.66}\mathrm{\;g}$ of 10 as a light yellow oil, yield 86%. ${}^{1}\mathrm{H}$ NMR (300 MHz, CDCl3) $\delta : {7.33} - {7.14} \; \left( {\mathrm{m},{10}\mathrm{H}}\right) ,{5.85} - {5.62}\left( {\mathrm{m},2\mathrm{H}}\right) ,{5.09}\left( {\mathrm{\;d}, J = {5.4}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${3.52}\left( {\mathrm{\;d}, J = {6.8}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{1.97}\left( {\mathrm{\;d}, J = {2.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (75 MHz, CDCl3) 6: 142.3, 135.3, 135.3, 130.4, 128.7, 128.4, 127.5, 126.6, 126.4, 126.1, 74.2, 36.0; IR (film) $v$ : 967,699,738 ${\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) m/z (%): 256 (27), 146 (49), 129 (29), 110 (100), 105 (80), 77 (52), 65 (15); HRMS calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{16}\mathrm{{OSNa}} \; {\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {279.0814}$ , found 279.0807.

(E)-2-(4-(Phenylthio)but-2-enyl)isoindoline-1,3-dione (1p): Triphenylphosphane (1.179 g, 4.5 mmol) and phthalimide (0.529 g, 3.6 mmol) were added at room temperature to a solution of ${0.540}\mathrm{\;g}$ (3 mmol) of (E)-4-(phenylthio)but-2-en-1-ol (1n) in THF (10 mL). Diethyl azodicarboxylate $\left( {{0.783}\mathrm{{mg}},{4.5}\mathrm{{mmol}}}\right)$ was added dropwise to the reaction mixture at $0{}^{ \circ }\mathrm{C}$ . After complete consumption (the reaction was monitored by TLC), the solvent was removed in vacuo and the crude product was purified by column chromatography on silica gel to afford the corresponding $\mathbf{{1p}}$ as a white solid, 0.917 g, yield 99%. m.p. 114-115 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ: 7.84-7.82 (m, 2H), 7.73-7.71 (m, 2H), 7.30-7.26 (m, 2H), 7.17-7.14 (m, 2H), 7.06- 7.02 (m, 1H), 5.81-5.75 (m, 1H), 5.56-5.51 (m, 1H), ${4.18}\left( {\mathrm{\;d}, J = {6.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.46}\left( {\mathrm{\;d}, J = {7.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (75 MHz, CDCl3) δ: 167.6, 135.0, 133.8, 132.0, 130.9, 129.7, 128.6, 126.5, 126.4, 123.2, 38.8, 36.2; IR (film) $v$ : 1709,1392,717 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {309}\left( {36}\right) ,{200}\left( {100}\right) ,{182}\left( {40}\right) ,{130}\left( {38}\right)$ , 109 (35),53 (49); HRMS calcd for ${\mathrm{C}}_{18}{\mathrm{H}}_{15}{\mathrm{{NO}}}_{2}\mathrm{{SNa}} \; {\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {332.0716}$ , found 332.0708.

(E)-2-(3-(Phenylthio)prop-1-enyl)-1,3-dioxolane (1q): To a 25 mL two-necked, round-bottomed flask, equipped with a Dean-Stark adapter and a condenser, containing the (E)-4-(phenylthio)but-2-enal (4) (0.534 g, 3 mmol), p-toluenesulfonic acid (14 mg, 0.075 mmol), in benzene (15 mL) was added ethylene glycol (0.279 g, 4.5 mmol) in benzene (10 mL). The reaction mixture was heated to reflux and was monitored by TLC until no starting aldehyde was detected. The reaction mixture was then filtered through a pad of anhydrous ${\mathrm{{NaHCO}}}_{3}$ , and the filter cake was washed with ${\mathrm{{CH}}}_{2}{\mathrm{{Cl}}}_{2}\left( {{10}\mathrm{\;{mL}} \times 3}\right)$ . Concentration of the filtrate gave the crude product which was further purified by column chromatography on silica gel to give 0.373 g of 1q as a light yellow oil, yield 56%. ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) 5: 7.34-7.16 (m, 5H), 3.96-3.83 (m, 4H), 5.97 (td, J=6.93, 6.93, 15.17 Hz, 1H), 5.57 (dd, $J = {5.8},{15.40}\mathrm{\;{Hz}},1\mathrm{H}),{5.21}\left( {\mathrm{\;d}, J = {5.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.55}$ (d, $J = {6.9}\mathrm{\;{Hz}},2\mathrm{H}$ ); ${}^{13}\mathrm{C}\mathrm{{NMR}}\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \; \delta : {135.5},{131.3},{129.9},{129.4},{128.8},{126.3},{102.8},{64.7}$ , 35.5; EI-MS (relative intensity) $m/z\left( \% \right) : {222}\left( {24}\right) ,{112}$ (100), 73 (47), 41 (87); IR (film) v: 1141, 1404, 961, 738,687 ${\mathrm{{cm}}}^{-1}$ ; HRMS calcd for ${\mathrm{C}}_{12}{\mathrm{H}}_{14}{\mathrm{O}}_{2}\mathrm{{SK}}$ (M + Na) ${}^{ + }$ : 261.0556, found 261.0552.

Synthesis and spectral data for products $2\mathrm{a} - 2\mathrm{q}$

General procedure for the reaction of allyl sulfides with chloramine-T: To a flask was added 1 mmol allyl sulfides (1), 1.3 mmol chloramine-T, 2 mL of EtOH and the system was stirred at the assigned temperature. After the reaction finished, the solvent was removed in vacuo and the residue was purified by column chromatography on silica gel to afford the corresponding product.

$N$ -Allyl-4-methyl- $N$ -(phenylthio)benzenesulfonamide (2a): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) δ: 7.80 $\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.39}\left( {\mathrm{\;d}, J = {7.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.20} \; \left( {\mathrm{m},5\mathrm{H}}\right) ,{5.71}\left( {\mathrm{{tdd}}, J = {6.5},{6.47},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , ${5.15}\left( {\mathrm{t}, J = {14.1},{14.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.15}\left( {\mathrm{\;d}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , 2.42 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ: 144.0, 137.0, 136.1, 132.3, 129.6, 128.9, 127.8, 127.4, 126.3, 119.6, 56.9, 21.5; IR (film) v: 1349, 1160, 827, 812, 659 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {319}\left( {{\mathrm{M}}^{ + },{13}}\right)$ , 164 (56), 109 (72), 91 (100), 65 (54), 56 (44), 41 (45); HRMS calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{17}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{\;K}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {358.0332}$ , found 358.0326.

$N$ -Allyl-4-methyl- $N$ -( $p$ -tolylthio)benzenesulfonamide (2b): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.80}$ (d, $J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}),{7.35}$ (d, $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.29}$ (d, $J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}),{7.12}\left( {\mathrm{\;d}, J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.71}(\mathrm{{tdd}}, J = \; {6.4},{6.4},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.16}\left( {\mathrm{{dd}}, J = {5.2},{21.1}\mathrm{\;{Hz}}}\right.$ , 2H), 4.12 (d, J =6.4 Hz, 2H), 2.42 (s, 3H), 2.33 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) δ: 143.9,138.2,136.4, 133.1, 132.6, 129.6, 129.5, 128.3, 127.8, 119.4, 56.7, 21.5, 21.1; IR (film) v: 1352, 1160, 827, 809, 659 cm ${}^{-1}$ ; EI-MS (relative intensity) m/z (%): 333 (13), 178 (67), 123 (100), 91 (57), 65 (27); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}\mathrm{\;N}$ - ${\mathrm{O}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ , found 356.0742 .

$N$ -Allyl-4-methyl- $N$ -( $o$ -tolylthio)benzenesulfonamide (2c): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.82} \; \left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.47}\left( {\mathrm{\;d}, J = {7.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.30}(\mathrm{\;d}$ , $J = {8.1}\mathrm{\;{Hz}},2\mathrm{H}),{7.22} - {7.18}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{7.11} - {7.06}\left( {\mathrm{\;m},}\right)$ 2H),5.71 (tdd, $J = {6.5},{6.5},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}$ ),5.13 (ddd, $J = {1.2},{13.6},{11.2}\mathrm{\;{Hz}},2\mathrm{H}$ ), ${4.16}(\mathrm{d}, J = {6.5}\mathrm{\;{Hz}}$ , 2H), 2.43 (s, 3H), 2.22 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {144.0},{136.2},{136.2},{132.8},{132.1},{130.1}$ , 129.6, 127.8, 126.6, 126.3, 124.4, 119.7, 56.9, 21.6, 18.8; IR (film) v: 1352,1166,827,812,659 cm ${}^{-1}$ ; EI-MS (relative intensity) m/z (%): 333 (27), 178 (80), 137 (40), 123 (74), 91 (100), 65 (46), 45 (69); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ , found 356.0749.

$N$ -Allyl- $N$ -(4-chlorophenylthio)-4-methylbenzenesul-fonamide (2d): White solid, m.p. 64-65°C; ${}^{1}\mathrm{H}$ NMR $\left. {\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.80}(\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.36} - \; {7.26}\left( {\mathrm{\;m},6\mathrm{H}}\right) ,{5.70}\left( {\mathrm{{tdd}}, J = {6.5},{6.5},{10.1},{16.7}\mathrm{\;{Hz}},1\mathrm{H}}\right)$ , 5.19-5.13 (m,2H),4.13 (d, $J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}),{2.44}(\mathrm{\;s}$ , 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {144.2},{136.0}$ , 135.6, 133.5, 132.2, 129.6, 129.0, 128.0, 127.7, 119.9, 77.3, 77.0, 76.7, 57.0, 21.5; IR (film) v: 1474, 1349, 1086,812,659 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : 353 (11), 198 (49), 143 (68), 91 (100), 108 (30), 65 (46); HRMS calcd for ${\mathrm{C}}_{16}{\mathrm{H}}_{16}{\mathrm{{ClNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 376.0202, found 376.0203.

$N$ -Allyl- $N$ -(4-methoxyphenylthio)-4-methylbenzene-sulfonamide (2e): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.79}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{7.52}(\mathrm{\;d}, J = {8.9}\mathrm{\;{Hz}}$ , 2H), 7.30 (d, $J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}),{6.85}\left( {\mathrm{\;d}, J = {8.9}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , 5.72 (tdd, $J = {6.4},{6.4},{10.1},{16.5}\mathrm{\;{Hz}},1\mathrm{H}),{5.17}$ (ddd, $J = {1.3},{9.3},{7.1}\mathrm{\;{Hz}},2\mathrm{H}),{4.08}\left( {\mathrm{\;d}, J = {6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{3.81}$ (s, 3H), 2.43 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta : {160.6},{143.7},{136.5},{133.6},{132.9},{129.5},{127.7},{126.5}$ , 119.1, 114.4, 56.3, 55.3, 21.5; IR (film) v: 1590, 1492, 1346,1245,1086,824,812,662 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {349}\left( {12}\right) ,{194}\left( {56}\right) ,{139}\left( {100}\right) ,{91}$ (50); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 372.0698, found 372.0699.

$N$ -(4-Chlorophenylthio)- $N$ -(cyclohex-2-enyl)-4-meth-ylbenzenesulfonamide (2f): White solid, m.p. 79-80 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.84}(\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}}$ , 2H), ${7.40}\left( {\mathrm{\;d}, J = {8.6}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.27}\left( {\mathrm{\;m},4\mathrm{H}}\right)$ , 5.77-5.73 (m, 1H), 4.92 (br s, 2H), 2.24 (s, 3H), 1.91-1.54 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) $\delta : {144.1},{132.6},{129.7},{128.8},{127.6},{126.8},{59.8},{24.2}$ , 21.5, 21.1; IR (film) v: 1474, 1355, 1166, 1086, 873, 814,729,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z$ (%): 393 (12), 313 (66), 91 (100), 65 (44), 41 (42); HRMS calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{20}{\mathrm{{ClNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {416.0516}$ , found 416.0512.

$N$ -(Cyclohex-2-enyl)-4-methyl- $N$ -(phenylthio)ben-zenesulfonamide (2i): White solid, m.p. 101-102 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.85}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.44}\left( {\mathrm{\;d}, J = {7.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.33} - {7.30}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.21} - \; {7.17}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{5.75} - {5.72}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{4.93} - {4.91}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , 2.24 (s, 3H), 1.90-1.57 (m, 6H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3})\delta$ :143.9,137.0,137.0,132.4,129.6,128.7, 127.6, 127.0, 126.6, 124.8, 59.8, 24.2, 21.5, 21.2; IR (film) $v$ : 1355,1163,873,854,812,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) m/z (%): 359 (2), 279 (59), 124 (100), 109 (37), 91 (66), 81 (34), 65 (44); HRMS calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {382.0906}$ , found 382.0905.

$N$ -(Cyclohex-2-enyl)- $N$ -(4-methoxyphenylthio)-4- methylbenzenesulfonamide (2j): Colorless oil; ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.83}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.57}(\mathrm{\;d}$ , $J = {8.8}\mathrm{\;{Hz}},2\mathrm{H}),{7.30}\left( {\mathrm{\;d}, J = {8.0}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{6.86}(\mathrm{\;d}, J = \; {8.9}\mathrm{\;{Hz}},2\mathrm{H}),{5.79} - {5.75}\left( {\mathrm{\;m},1\mathrm{H}}\right) ,{5.04}\left( {\mathrm{\;s},\mathrm{{br}},1\mathrm{H}}\right)$ , 4.83-4.81 $\left( {\mathrm{m},1\mathrm{H}}\right) ,{3.81}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{2.43}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.95} - \; {1.59}\left( {\mathrm{\;m},6\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR $\left( {{100}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {159.9}$ , 143.6, 137.4, 131.9, 129.5, 127.7, 127.6, 114.3, 59.7, 55.3, 24.3, 21.5, 21.3; IR (film) v: 1590, 1492, 1346, 1251, 1160, 1083, 1028, 873, 854, 812, 729, 665 cm ${}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : ${389}\left( 5\right) ,{309}\left( {36}\right)$ , 154 (100), 139 (74), 91 (56), 65 (26); HRMS calcd for ${\mathrm{C}}_{20}{\mathrm{H}}_{24}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}{\left( \mathrm{M} + \mathrm{H}\right) }^{ + } : {390.1192}$ , found 390.1191.

$N$ -Allyl- $N$ -(butylthio)-4-methylbenzenesulfonamide (2k): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta$ : 7.80 $\left( {\mathrm{d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.30}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{5.77}(\mathrm{{tdd}}$ , $J = {6.5},{6.5},{10.08},{16.7}\mathrm{\;{Hz}},1\mathrm{H}),{5.19}(\mathrm{{ddd}}, J = {1.3}$ , ${10.9},{8.7}\mathrm{\;{Hz}},2\mathrm{H}),{4.04}\left( {\mathrm{\;d}, J = {6.5}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.88}(\mathrm{t}, J = \; {7.4}\mathrm{\;{Hz}},2\mathrm{H}),{2.43}\left( {\mathrm{\;s},3\mathrm{H}}\right) ,{1.59} - {1.52}\left( {\mathrm{\;m},2\mathrm{H}}\right)$ , ${1.43} - {1.36}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,\left( {\mathrm{t}, J = {7.33},{7.33}\mathrm{\;{Hz}},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) $\delta$ : 143.6, 136.0, 133.1, 129.4, 127.8, 119.1, 57.6, 39.8, 29.1, 21.8, 21.5, 13.6; IR (film) v: 1345, 1160, 1089, 912, 827, 812, 732, 662 cm ${}^{-1}$ ; EI-MS (relative intensity) m/z (%): 299 (30), 344 (52), 103 (70), 91 (100), 65 (44), 56 (97), 41 (70), 29 (53); HRMS calcd for ${\mathrm{C}}_{14}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {322.0907}$ , found 322.0906.

$N$ -Allyl- $N$ -(benzylthio)-4-methylbenzenesulfonamide (21): White solid, m.p. 52—53 °C; ${}^{1}$ H NMR (400 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {7.82}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.32} - {7.26}\left( {\mathrm{\;m},7\mathrm{H}}\right)$ , ${5.52}\left( {\mathrm{{tdd}}, J = {6.5},{6.5},{10.4},{16.8}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.06} - {5.01} \; \left( {\mathrm{m},2\mathrm{H}}\right) ,{4.10}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{3.81}\left( {\mathrm{\;d}, J = {6.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.42}(\mathrm{\;s}$ , 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) $\delta : {143.7},{136.2}$ , 134.9, 132.7, 129.7, 129.4, 128.6, 127.8, 127.6, 118.9, 57.2,44.8,21.5; IR (film) $v : {1349},{1160},{1086},{925},{827}$ , ${812},{711},{699},{662}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z$ (%): 333 (10), 123 (20), 91 (100), 65 (19); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{19}{\mathrm{{NO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {356.0749}$ , found 356.0741.

$N$ -(1-Bromobut-3-en-2-yl)-4-methyl- $N$ -(phenylthio)- benzenesulfonamide (2m): White solid, m.p. 83-84 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta : {7.83}\left( {\mathrm{\;d}, J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${7.52}\left( {\mathrm{\;d}, J = {7.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.34} - {7.23}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{5.64}(\mathrm{{ddd}}$ , $J = {7.8},{10.3},{17.3}\mathrm{\;{Hz}},1\mathrm{H}),{5.15}\left( {\mathrm{\;d}, J = {10.4}\mathrm{\;{Hz}},2\mathrm{H}}\right)$ , ${4.91}\left( {\mathrm{q}, J = {7.4},{7.4},{7.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{3.45}(\mathrm{{dd}}, J = {6.9},{10.4} \; \mathrm{{Hz}},1\mathrm{H}),{3.34}\left( {\mathrm{t}, J = {8.7},{8.7}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{2.42}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) δ: 144.2, 137.7, 136.1, 133.2, 129.4, 128.9, 128.1, 127.7, 126.6, 120.6, 66.0, 32.1, 21.6; IR (film) v: 1358, 1163, 1086, 888, 836, 812, 741, ${668}{\mathrm{\;{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {413}\left( 8\right)$ , 411 (7), 258 (37), 256 (36), 124 (44), 109 (69), 91 (100), 65(63); HRMS calcd for ${\mathrm{C}}_{17}{\mathrm{H}}_{18}{\mathrm{{BrNO}}}_{2}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + }$ : 433.9855, found 433.9847.

$N$ -(1-Hydroxybut-3-en-2-yl)-4-methyl- $N$ -(phenyl-thio)benzenesulfonamide (2n): White solid, m.p. 107-108 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl ${}_{3}$ ) $\delta : {7.83}$ (d, $J = {8.3}\mathrm{\;{Hz}},2\mathrm{H}),{7.58}\left( {\mathrm{\;s},2\mathrm{H}}\right) ,{7.36} - {7.24}\left( {\mathrm{\;m},5\mathrm{H}}\right) ,{5.56} \; \left( {\mathrm{{ddd}}, J = {8.0},{10.0},{17.6}\mathrm{\;{Hz}},1\mathrm{H}}\right) ,{5.09}(\mathrm{\;d}, J = {10.5}\mathrm{\;{Hz}}$ , 2H), 4.81 (dt, $J = {5.3},{8.0},{7.7}\mathrm{\;{Hz}},1\mathrm{H}),{3.70}(\mathrm{t}, J = {10.0}$ ,

$N$ -(1-Hydroxy-1-phenylbut-3-en-2-yl)-4-methyl- $N$ - (phenylthio) benzenesulfonamide (20): Colorless oil; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) δ: 7.84 (d, J=8.2 Hz, 2H), 7.74-7.69 (m, 2H), 7.37-7.21 (m, 10H), 5.52 (ddd, $J = {8.4},{10.4},{17.2}\mathrm{\;{Hz}},1\mathrm{H}),\left( {\mathrm{d}, J = {10.1}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{4.70}(\mathrm{\;s}$ , 1H), 4.57 (s, 1H), 2.39 (s, 3H), 2.30 (s, 1H); ${}^{13}\mathrm{C}$ NMR (100 MHz, CDCl ${}_{3}$ ) δ: 144.0, 139.6, 137.5, 136.0, 131.7, 129.2, 129.1, 128.3, 128.1, 128.1, 127.6, 127.4, 120.7, 74.0, 71.7, 21.5; IR (film) v: 1346, 1160, 1086, 1022, 906,812,732,699,668 cm ${}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right) : {318}\left( {32}\right) ,{210}\left( {98}\right) ,{163}\left( {69}\right) ,{155}\left( {48}\right) ,{109}$ (47), 91 (100), 79 (52), 65 (44); HRMS calcd for ${\mathrm{C}}_{23}{\mathrm{H}}_{23}{\mathrm{{NO}}}_{3}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {448.1011}$ , found 448.1003.

$N$ -(1-(1,3-Dioxoisoindolin-2-yl)but-3-en-2-yl)-4- methyl- $N$ -(phenylthio)benzenesulfonamide (2p): White solid, m.p. 183-185 °C; ${}^{1}\mathrm{H}$ NMR (400 MHz, CDCl3) $\delta : {7.78} - {7.75}\left( {\mathrm{\;m},4\mathrm{H}}\right) ,{7.71} - {7.68}\left( {\mathrm{\;m},2\mathrm{H}}\right) ,{7.46}\left( {\mathrm{\;s},2\mathrm{H}}\right)$ , 7.30-7.11 (m, 5H), 5.77-5.68 (m, 1H), 5.22-5.03 $\left( {\mathrm{m},3\mathrm{H}}\right) ,{3.83}\left( {\mathrm{\;d}, J = {13.4}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{2.26}\left( {\mathrm{\;s},3\mathrm{H}}\right) ;{}^{13}\mathrm{C}$ NMR (100 MHz, CDCl3) 5: 167.7, 143.8, 138.3, 133.9, 131.8, 129.4, 128.7, 127.8, 127.1, 125.8, 123.2, 120.4, 120.3, 62.4, 39.9, 21.5; EI-MS (relative intensity) $m/z$ (%): 478 (2), 318 (30), 200 (24), 160 (100), 91 (49); HRMS calcd for ${\mathrm{C}}_{25}{\mathrm{H}}_{22}{\mathrm{\;N}}_{2}{\mathrm{O}}_{4}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {501.0905}$ , found 501.0913.

$N$ -(1-(1,3-Dioxolan-2-yl)allyl)-4-methyl- $N$ -(phenyl-thio)benzenesulfonamide (2q): Colorless oil; ${}^{1}\mathrm{H}$ NMR $\left( {{400}\mathrm{{MHz}},{\mathrm{{CDCl}}}_{3}}\right) \delta : {7.82}\left( {\mathrm{\;d}, J = {8.2}\mathrm{\;{Hz}},2\mathrm{H}}\right) ,{7.47}(\mathrm{\;s}$ , 2H), 7.30-7.12 (m, 5H), 5.82 (ddd, J=7.8, 10.4, 17.9 Hz, 1H), 5.19 (d, J = 10.5 Hz, 2H), 5.01 (s, 1H), 5.01-4.69 (m, 1H), 3.86-3.83 (m, 4H), 2.41 (s, 3H); ${}^{13}\mathrm{C}$ NMR (100 MHz, ${\mathrm{{CDCl}}}_{3}$ ) 6: 143.8,138.2,136.3, 131.4, 129.2, 128.5, 128.2, 126.9, 125.6, 120.8, 103.1, 65.9, 65.3, 64.5, 21.5; IR (film) v: 1349, 1163, 1086, 866,814,665 ${\mathrm{{cm}}}^{-1}$ ; EI-MS (relative intensity) $m/z\left( \% \right)$ : 282 (8), 109 (11), 91 (14), 73 (100), 45 (23); HRMS calcd for ${\mathrm{C}}_{19}{\mathrm{H}}_{21}{\mathrm{{NO}}}_{4}{\mathrm{\;S}}_{2}\mathrm{{Na}}{\left( \mathrm{M} + \mathrm{{Na}}\right) }^{ + } : {414.0804}$ , found 414.0800.

Acknowledgement

The project is supported by NSFC (Nos. 20902005, 20832002, 20772003, 20821062) and 973 Program (No. 2012CB821600).

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