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Reactions of Sulfonyl Chlorides and Unsaturated Compounds

Simin Sun , Jiaxi Xu

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (6) : 1275 -1289.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (6) : 1275-1289 DOI: 10.7536/PC210902
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Reactions of Sulfonyl Chlorides and Unsaturated Compounds
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Abstract

Sulfonyl chlorides are a class of important organic synthetic intermediates and have been widely applied in organic and medicinal synthesis. Sulfonyl chlorides have been utilized in organic reactions as important and powerful sources of sulfenes, sulfonyl, sulfenyl, aryl, and fluorinated alkyl groups. Reactions of sulfonyl chlorides with alkenes, alkynes, (hetero)aromatics, imines, halogenated aldehydes and ketones, and other unsaturated compounds are summarized in this review, including mainly [2+2] annulations, chlorosulfonylation, sulfonylation, sulfenylation, arylation, and fluoroalkylation. The further development on the reactions of sulfonyl chlorides and unsaturated compounds are discussed and predicted.

Contents

1 Introduction

2 Reactions of sulfonyl chlorides with alkenes,alkynes and(hetero)arenes

2.1 Annulations

2.2 Radical reactions

2.3 Ionic reactions

3 Reactions of sulfonyl chlorides with imines

4 Reactions of sulfonyl chlorides with aldehydes/ketones

5 Reactions of sulfonyl chlorides with other unsaturated compounds

6 Conclusion and outlook

Graphical abstract

Keywords

sulfonyl chloride / alkene / alkyne / aromatic / imine / aldehyde / ketone

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Simin Sun, Jiaxi Xu. Reactions of Sulfonyl Chlorides and Unsaturated Compounds. Progress in Chemistry, 2022, 34(6): 1275-1289 DOI:10.7536/PC210902

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1 Introduction

Sulfonyl chloride is an important intermediate in organic synthesis and is widely used in the preparation of drugs and pesticides containing sulfonamide pharmacophore, such as anticancer drugs, antitumor drugs, anti-HIV drugs, antiviral drugs, antidepressants and antipsychotics (Fig. 1)[1⇓⇓~4]. Sulfonyl chloride is widely used in the preparation of sulfonamide drugs because of its cheapness, easy preparation and high reactivity, and is also often used to activate hydroxyl groups for further substitution reactions[5⇓⇓⇓~9][10]. In addition, sulfonyl chloride can also react with a variety of compounds containing unsaturated bonds. For example, in the presence of base, alkylsulfonyl chloride can react with alkenes, alkynes, imines, aldehydes, ketones and other compounds containing unsaturated bonds to form the corresponding quaternary products. Recently, it has been found that sulfonyl chloride can also introduce sulfonyl, sulfenyl and alkyl groups into olefins, alkynes and aromatics through free radical reactions catalyzed by cuprous chloride, which opens up new applications of sulfonyl chloride.
In this paper, the reactions of sulfonyl chloride with alkenes, alkynes, (hetero) aromatic rings, imines, aldehydes and ketones, and azo compounds are reviewed according to the classification of unsaturated systems.

2 Reaction of sulfonyl chloride with alkene, alkyne, (hetero) aromatic ring

There are many reactions of sulfonyl chloride with alkenes, alkynes and aromatic compounds, which will be classified according to the reaction mechanism, and the development of cyclization reaction, free radical reaction and ionic reaction will be introduced.

2.1 Cyclization reaction

In 1962, Truce et al. Found that alkylsulfonyl chloride 1 reacted with 1,1-dialkoxyethylene 2 in ether with triethylamine as a base to produce 3,3-dialkoxysulfolane 3 (Scheme 1)[11]. In the presence of triethylamine, sulfonyl chloride 1 first eliminates hydrogen chloride to form vinyl sulfone 4, which then undergoes cyclization with 1,1-dialkoxyethylene 2 to form 3,3-dialkoxysulfolane 3. From then on, the exploration of the reaction of sulfonyl chloride with unsaturated system was opened. Over the next 30 years, Truce et al., Paquette et al., and Shipov et al. Have published a number of similar reactions of alkylsulfonyl chloride with ketene ketals, expanding the scope of substrates[12⇓⇓⇓⇓~17].
In 1962, Stork et al. And Opitz et al. Reported the cyclization of alkylsulfonyl chloride 1 with enamine 5 formed by morpholine, piperidine and aldehydes and ketones to produce 3-dialkylamino sulfolane 6[18,19]. Later, Paquette et al., Abbott et al. Also reported similar cyclization reactions of alkylsulfonyl chloride 1 with enamine 5 formed by dimethylamine, diethylamine, tetrahydropyrrole, piperidine, morpholine, and N-methylpiperazine with aldehydes and ketones (Scheme 2), enriching the scope of reactions of sulfonyl chloride with electron-rich olefins[20⇓⇓⇓⇓~25][26⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~40].
Following the cyclization reaction of alkylsulfonyl chloride with electron-rich alkenes such as enol ethers and enamines, Eckroth et al. And Rosen successively obtained sulfolene derivative 8 by the reaction of alkylsulfonyl chloride 1 with N, N-dimethylprop-1-yn-1-amine 7 in 1969 (Scheme 3)[41,42].
The reaction of alkylsulfonyl chloride with electron-deficient enynes has not been reported. Recently, our group found that under the condition of pyridine as a base, alkylsulfonyl chloride 1 could react with electron-deficient alkyne acetylenic diacid ester 9 to form the corresponding sulfolene derivative 10, accompanied by the formation of ring-opening by-product 11 (Scheme 4)[43]. Unfortunately, the yield is not high, but it is the first cyclization reaction of sulfonyl chloride with electron-deficient alkyne.

2.2 Free radical reaction

2.2.1 Preparation of sulfone compound

Sulfone is an important structural unit in natural products and pharmaceuticals. The radical addition of sulfonyl chloride to alkenes and alkynes can realize the 1,2-chlorosulfonylation of enynes to give sulfones.
Goralski et al. Developed the reaction of arylsulfonyl chloride 12 with arylvinyl compound 13 to produce vinyl sulfone compound 14[44]; Or the chloroethyl sulfone compound 15 is generated first, and the vinyl sulfone compound is regenerated by alkali heating treatment (scheme 5). From then on, the method of sulfonyl chloride radical addition to prepare sulfone compounds, thioether compounds and fluoroalkyl compounds was initiated. Recently, Wang et al. Also achieved this reaction with Cu(OTf)2 catalysis[45].
In 1983, Kamigata et al. Reported the radical addition of arylsulfonyl chloride 12 to terminal alkene 16 (Scheme 6)[46]. Under the catalysis of RuCl2(PPh3)3, chloroethyl sulfone 15 was obtained with the highest yield of 99%. In this reaction, Ru (Ⅱ) first reduces sulfonyl chloride to form sulfonyl radical intermediate 17, then 17 adds to terminal ene 16 to form intermediate 18, and finally 18 reacts with Ru (Ⅲ) -Cl to form the target product 15. If trichloromethanesulfonyl chloride is used as a reactant, the sulfone radical intermediate will lose its SO2 to form a trichloromethyl radical intermediate, which will eventually form a trichloromethylated product.
In 2005, Liang et al. Developed the reaction of sulfonyl chloride 19 with alkyne 20 (Scheme 7)[47]. The syn-β-chlorovinyl sulfone 21 was obtained under CuCl catalysis at 110 ° C with Me2S as an additive. In this reaction, intermediate A is formed through a free radical mechanism, and the additive Me2S has the effect of stabilizing intermediate A. The reaction can synthesize cis-vinyl sulfone in one step and has the advantage of good stereoselectivity. Unfortunately, only aryl-terminated alkynes are used as substrates, and the yield of disubstituted alkynes as substrates will decrease or even not react.
In 2018, Reiser et al. Realized the copper-catalyzed reaction of sulfonyl chloride 19 with terminal alkene 16 and alkyne 20 (Scheme 8)[48]. The reaction occurred under visible light, catalyzed by [Cu(dap)2]Cl(Ⅰ) or [Cu(dap)Cl2](Ⅱ), and finally produced chloroethyl sulfones 15 as well as β-chlorovinyl sulfones 21. The reaction mechanism is similar to the previous one, in which the excited copper catalyzes sulfonyl chloride to generate chlorine radical and sulfonyl radical, and then the subsequent photocatalytic reaction is carried out. The alkenyl sulfone can be obtained by unimolecular elimination of product 15.
Nakamura et al. Reported the reaction of arylsulfonyl chloride 12 with terminal alkyne 22 in 2011 (Scheme 9)[49]. Iron catalyst and phosphine ligand initiated the formation of sulfonyl radical at high temperature, followed by radical addition, resulting in a single (E) -β-chlorovinyl sulfone 23 with a maximum yield of 92%. Recently, Li and Jiang et al. Have achieved the synthesis of (E) -β-iodovinyl sulfones via iodine-initiated such reactions[50].
In 2020, Li et al. Synthesized vinyl sulfone 25 by sulfonylation of sp2C-H bond through sulfonylation of sulfonyl chloride 19 and arylethene 24 mediated by hypervalent iodine reagent (Figure 10)[51]. In the reaction, the hypervalent iodine reagent first initiates sulfonyl chloride to form sulfonyl radical intermediate 17, which reacts with olefin 24 to form intermediate 26, then 26 reacts with sulfonyl chloride 19 to form β-chlorosulfone 15, and finally 15 eliminates HCl with benzoate as a base to form vinyl sulfone 25. The reaction was carried out under metal-free, mild and neutral conditions and showed good air and moisture tolerance, and vinyl sulfones could be obtained in moderate to good yields, providing a novel and facile strategy for the synthesis of vinyl sulfones.
In 2016, Reiser et al. Developed fac[Ir(ppy)3] as a photocatalyst to catalyze the reaction of sulfonyl chloride 19 with alkene 27 (Fig. 11)[52]. In addition to changing the catalyst, water was added to the solvent, resulting in β-hydroxysulfone compound 28. The sulfonyl radical intermediate 17 was formed first, followed by the addition of 17 to olefin 27 to form intermediate 29, which was oxidized by catalyst to form cationic intermediate 30, and finally the nucleophilic attack of water on 30 to form the target product 28 in 62% ~ 97% yield. If cyclic olefin was used, the product could be obtained stereoselectively with trans ∶ cis = 9 ∶ 1.
Because β-carbonyl sulfone compounds have important medicinal value, in 2017, Niu et al. Published the reaction of synthesizing β-carbonyl sulfone 31 with sulfonyl chloride 19, terminal alkene 16 and terminal alkyne 22 under the conditions of visible light, air and Ir(ppy)2(dtbbpy)PF6 (Figure 12)[53,54]. In the reaction, sulfonyl radical is first generated, which is added with alkene and alkyne, and finally oxidized by oxygen in the air to obtain carbonyl, which is used to generate the target product β-carbonyl sulfone compound through subsequent reactions. Oxygen in the air is skillfully used as an oxidant in the reaction, and the reaction has good functional group tolerance, so that the target product is obtained in a moderate to excellent yield.
In 2019, Zhao et al. Reported the reaction of arylsulfonyl chloride 12 with N-propargyl indole 32 to give 9H-pyrrolo [1,2-a] indoles 33 under visible light irradiation fac-Ir(ppy)3 catalysis with Na2CO3 as a base (Scheme 13)[55]. The sulfonyl radical 17b generated in situ from sulfonyl chloride adds to alkyne to form intermediate 34, followed by intramolecular cyclization to form intermediate 35, which undergoes one-electron redox to form cationic intermediate 36, further elimination to form 37, and finally isomerization to form the target product 33. The reaction has the advantages of simple operation, good functional group tolerance and easy preparation of raw materials, and is a simple and effective method for the preparation of functionalized 9H-pyrrolo [1,2-a] indoles.

2.2.2 Preparation of thioether compound

In addition to the synthesis of the above sulfone compounds, sulfonyl chloride can also react with unsaturated compounds such as alkenes, alkynes, (hetero) aromatic rings, etc. In the presence of a reducing reagent to produce thioether compounds.
In 2011, You et al. Realized the aromatic C — H bond aryl sulfidation reaction with triphenylphosphine as a reducing agent at 130 ℃[56]. Arylsulfonyl chloride 12 reacts with aromatic compounds 38 such as indolizidines, indoles, electron-rich benzenes to produce diaryl or heteroaryl sulfides 39 (Scheme 14). Arylsulfonyl chloride 12 is first reduced by triphenylphosphine to form sulfenyl chloride 40, which is then attacked by indolizine 41 to form amphoteric intermediate 42, which is then eliminated by HCl to form diaryl sulfide 39. The reaction has the advantages of no need of noble metal catalyst, low cost and the like, and lays a good foundation for the aryl sulfurization of the aryl C — H bond.
In 2012, Zheng et al. Used arylsulfonyl chloride 12 and N-methylindole 44 as raw materials to obtain 3-arylthio N-methylindole 45 in moderate yield under the irradiation of fluorescent lamp and the catalysis of Ru(bpy)3Cl2 (Fig. 15)[57].
In 2019, Deng et al. Carried out the arylsulfidation reaction of arylsulfonyl chloride 12 with α-methoxy or aminonaphthalene 46 C — H bond in oxygen, solvent-free, diethyl phosphite and tetramethylammonium iodide (TMAI) to obtain diaryl sulfide 47 (Scheme 16)[58]. Sulfonyl chloride is first reduced to sulfenyl chloride by diethyl phosphite, and then sulfenyl iodide is obtained by the attack of iodide ion, which is heated to form arylsulfide radical to continue the radical reaction. The method uses readily available aryl sulfonyl chloride as an aryl sulfurization reagent to carry out direct aryl sulfurization on aromatic compounds, and the reaction is metal-free and solvent-free, thereby providing a simple, green and economical way for synthesizing multifunctional diaryl sulfide.
Yi et al. Used copper catalysis in the triphenylphosphine system to supplement the synthesis of β-chlorothioethers by copper-catalyzed S — Cl bond homolysis (Figure 17)[59,60]. Sulfonyl chloride 19 was used to react with alkyne 20 and terminal alkene 16, respectively, to produce β-chloroalkenyl sulfide 48 and β-chloroalkyl sulfide 49 under Cu-catalyzed conditions with PPh3 as a reducing agent.

2.2.3 Preparation of fluoroalkylated product

With the rapid development of photochemical redox and the application of trifluoromethyl-containing aromatic compounds in medicinal chemistry, the radical addition of fluoroalkylsulfonyl chlorides as fluoroalkyl sources to alkenes and alkynes has also been developed.
In 2011, MacMillan et al. Combined trifluoromethanesulfonyl chloride 50a as a reactant with photocatalysis under the conditions of illumination, Ru(phen)3Cl2 catalysis and K2HPO4 as base, and reacted with six-membered aromatic (heterocyclic) ring 51 and five-membered aromatic heterocyclic ring 52 to successfully obtain aromatic heterocyclic C — H bond trifluoromethylation products 53 and 54 (Fig. 18)[61]. In the reaction, the excited Ru2+ first transfers an electron to trifluoromethanesulfonyl chloride 50a to form a radical anion intermediate 55, which quickly removes a molecule of SO2 and chloride anion to form a trifluoromethyl radical 56, which adds to the 51 a radical to form an intermediate 57, which is then oxidized by Ru3+ to form a cation intermediate 58, and finally 58 leaves a hydrogen proton to form the target product 53 a. The reaction has the advantages of wide substrate range, strong functional group tolerance and mild conditions, and is a new way of trifluoromethylation.
Inspired by this, studies on the construction of C — C bonds by the reaction of sulfonyl chloride as an aryl source with (hetero) aromatic rings have also been developed. In 2016, Natarajan et al. And Reiser et al. Used fac-[Ir(ppy)3] as photocatalyst to arylate the 2-position of pyrrole, furan, thiophene, N-methylpyrrole and other heteroaromatic rings with aryl sulfonyl chloride[62][63].
In 2013, Han et al. Reported the reaction of trifluoromethanesulfonyl chloride 50a with olefin 59 (Scheme 19)[64]. Under the conditions of visible light irradiation, Ru(Phen)3Cl2 catalysis and K2HPO4 as an additive, the o-chloro-trifluoromethylated product 60 can be obtained in excellent yield. The reaction also proceeds through a radical process, with trifluoromethylsulfonyl chloride 50a first generating a trifluoromethyl radical 56,56 adding to olefin 59 to generate a radical intermediate 61,61 being oxidized to generate a cation intermediate 62, and finally chloride attacking 62 to generate product 60a.
In 2014, Dolbier et al. Realized the radical cyclization reaction of fluoroalkylsulfonyl chloride 50 with N-arylacrylamide 63 (Scheme 20)[65]. Under the conditions of visible light irradiation, Ru(phen)3Cl2 or fac-Ir(ppy)3 catalysis, and in the presence of K2HPO4, 3,3-disubstituted indolidinone compound 64 with fluoroalkyl at the 3-position can be produced in high yield. The reaction also undergoes radical initiation, intramolecular cyclization, and finally reductive aromatization with hydrogen proton elimination.
In the same year, they also conducted an in-depth study on the formation of fluoroalkyl radicals from fluoroalkylsulfonyl chloride, and under the conditions of irradiation, Cu(dap)2Cl catalysis, and K2HPO4 as an additive, fluoroalkylsulfonyl chloride 50 reacted with electron-deficient olefin 65 to obtain fluoroalkyl compound 66 in high yield (Fig. 21)[66]. The reaction is a free radical mechanism. The product α-chloro-β-fluoro derivative has an active C — Cl bond, which can be further converted into fluorinated amino acids, olefins and other useful derivatives, and has a wide range of applications.
In 2015, they developed a nonmetal-catalyzed reaction of α-bisfluorosulfonyl chloride 50 with terminal alkene 16 (Scheme 22)[67]. Under the initiation of dilauroyl peroxide DLP, the difluoromethylated product 69 of olefin was formed. Unfortunately, the electron-deficient olefin yield is low.

2.2.4 Preparation of sulfonic acid derivatives

With the development of photochemistry, Reiser et al. Reported the reaction of trifluoromethanesulfonyl chloride 50a with terminal alkene 16 (Scheme 23)[68,69]. Under the conditions of green light irradiation, [Cu(dap)2]Cl catalyst and K2HPO4 as an additive, the trifluoromethylchlorosulfonylation product 70 of olefins could be obtained. Excited Cu reacts with reactant 50a to form trifluoromethyl radical 56 and Cu-SO2Cl intermediate, then 56 reacts with olefin to form alkyl radical intermediate 71, and finally 71 captures the sulfonyl group of Cu-SO2Cl to form product 70. The main function of the [Cu(dap)2]Cl is to catalyze the generation of sulfonyl chloride free radicals and generate Cu-SO2Cl intermediates to prevent the SO2 from leaving and ensure the occurrence of the bifunctional group reaction. This is the first report of visible light-mediated trifluoromethylchlorosulfonylation of non-activated alkenes with trifluoromethanesulfonyl chloride, which can selectively give sulfonyl chloride products.
They continued their research and found that under the same reaction conditions, the substrate olefin was replaced by α, ω-enol 72, which reacted with trifluoromethanesulfonyl chloride 50a to produce α-trifluoroethyl sultone 73 (Scheme 24)[70]. The reaction mechanism is similar to that of Scheme 23, except that the hydroxyl oxygen undergoes an intramolecular nucleophilic substitution reaction with sulfonyl chloride at the end. The yield of six-membered sultone is high, and the yield of β-sultone is very low when there is a substituent at the α-position of the hydroxyl carbon.

2.3 Ionic reaction

In addition to the above radical reactions, sulfonyl chloride can also react ionically with olefins. Metal catalyzed cross-coupling reactions with alkynes, alkenes, arenes, etc. Can be carried out using sulfonyl chloride as the alkyl source and aryl source. Metal-catalyzed cross-coupling reactions of sulfonyl chlorides were discovered and extensively studied in the 20th century, and sulfonyl chlorides have been widely used in Pd- and Rh-catalyzed Mizoroki-Heck reactions. There are relatively few reports in the past two decades, and this paper chooses to introduce the representative results.
In 2004, Vogel et al. Reported the reaction of aryl sulfonyl chloride 12 with terminal alkyne 22 under the conditions of metallic palladium – copper co-catalysis and base as an additive, and finally the product alkyne 20 of Sonogashira-Hagihara cross-coupling was obtained in moderate to excellent yield (Scheme 25)[71]. The possible mechanism of the reaction is as follows: first, the S — Cl bond of arylsulfonyl chloride 12 undergoes oxidative addition to form Pd (Ⅱ) intermediate 74 by Pd0, then the Pd (Ⅱ) intermediate 74 rapidly loses a molecule of SO2 to form intermediate 75, which then undergoes a transmetallation reaction with copper alkyne intermediate 76 to form intermediate 77, and finally the target product 20 is obtained by reductive elimination. The reaction overcomes the disadvantage that the use of copper promoter inhibits the reaction of aryl chloride, tosylate and terminal alkyne in the same kind of cross-coupling.
A year later, they again reported a desulfo-Mizoroki-Heck type coupling reaction of aryl sulfonyl chloride 12 with terminal alkene 16 (Scheme 26)[72]. Under the condition of palladium catalysis and base as an additive, the coupled olefin product 24 was obtained. The reaction has the advantages of wide substrate range, low cost and the like, and is suitable for both monosubstituted and disubstituted olefins. It is worth mentioning that the reaction can also occur under alkali-free and phosphorus-free conditions using a rhodium catalyst.
In 2006, they modified the palladium-catalyzed desulfurization Mizoroki-Heck type coupling reaction in a nitrile-functionalized ionic liquid[73]. The solubility of the catalyst can be increased and the reaction time can be shortened. For olefins conjugated with carbon-carbon double bonds or aromatic rings, the yield will be improved.
Sulfonyl chloride can also react with alkenes and alkynes by ionic mechanism to form sulfones and thioethers. In 2004, Xi et al. Reported the reaction of sulfonyl chloride 19, terminal olefin 78, and water or methanol (Scheme 27)[74]. β-Hydroxysulfone derivative 79 was finally produced in moderate to excellent yield under acid-catalyzed conditions. It is presumed to provide a more reactive electrophile 80 for the protonation of the oxygen atom in the sulfonyl chloride, which in turn is attacked by the alkene to produce a benzylic carbocation 81, which subsequently undergoes deprotonation to form oxathietane 82. Further ring opening by a protic compound, such as water or alcohol, produces intermediate 83, which finally undergoes hydrogen proton transfer and elimination by HCl or RCl sequentially to give hydroxysulfone derivative 79.
In 2016, Yan et al. Reacted arylsulfonyl chloride 12 with phenol, indole and other heteroaromatic rings 85 at 100 ℃ in TBAI-HBr system to obtain diaryl sulfide product 86 (Figure 28)[75]. By using the TBAI-HBr system, phenol, indole and related heteroaromatic thioether derivatives can be easily prepared from inexpensive and easily prepared arylsulfonyl chloride as a sulfur source, and highly regioselective arylsulfide products can be produced in moderate to good yields in a shorter time, which provides a new method for the preparation of thioethers.
Sulfonyl chloride can react with aromatic compounds to form not only di (hetero) aryl sulfides, but also sulfides with an alkyl end. In 2016, Yi et al. Reported the reaction of fluoroalkylsulfonyl chloride 50 with indole, pyrrole, electron-rich benzene, (hetero) aromatic ring 87 (Scheme 29)[76]. (Hetero) aromatic ring C — H bond fluoroalkane sulfidation product 88 was obtained at 90 ℃ in the presence of (EtO)2P(O)H as a reducing agent. In the reaction, diethyl phosphite first reduces 50 to sulfenyl chloride 89, then the heteroaromatic ring attacks 89 to form intermediate 90, and finally HCl leaves to form the target product 88 a. An inexpensive electrophilic trifluoromethyl sulfurization method has been developed, which has a simple system and potential for large-scale use, but unfortunately can only be used in electron-rich aromatic systems. The reaction can also synthesize disulfides using sulfonyl chloride as the sulfur source.
In 2018, they continued to explore the reaction of sulfonyl chloride with olefins in depth. The reaction of fluoroalkylsulfonyl chloride 50 with terminal olefin 16 at 90.d egree. C. in the presence of PPh3 as a reducing agent resulted in o-chlorofluoroalkyl sulfurized product 91 (Scheme 30)[77]. First, 50 was reduced by triphenylphosphine to form sulfenyl chloride 89, and then electrophilic addition of 89 to arylethene 16 to form thionium intermediate 92. Finally, chloride ion regiospecifically opened the nucleophilic ring at the aromatic methyl position of 92 to form the target product 93. The electrophilic addition of 89 to aliphatic terminal alkene 16 results in the formation of thionium intermediate 94, which can be opened by chlorine anion to form Markovnikov addition product 91 and anti-Markovnikov addition product 95, but the anti-Markovnik addition product 95 is dominant. The same applies if the reactant is an alkyne or difluoromethanesulfonyl chloride. The reaction has the advantages of high efficiency, simplicity, good atom economy and the like.

3 Reaction of sulfonyl chloride with imine

Since the first reported preparation of β-sultam in 1960, chemists have studied β-sultam extensively, not only for its important biological properties, but also for its usefulness as a versatile reactive synthetic component[78]. As a four-membered ring system, β-sultam is a compound with high twist tension, and its CSN angle is about 81 °. While the chain sulfonamide is about 113 °[79]. Due to the structural distortion as well as less resonance stabilization than their β-lactam analogs, β-sultams are at least two orders of magnitude more reactive for nucleophilic ring opening than β-lactams, despite being UNK 1-fold faster in acyl transfer ability than sulfonyl transfer[80]. Compared with the ability of the corresponding chain sulfonamide to acid-base-catalyze hydrolytic S — N bond cleavage, the rate of β-sultam is at least 107 to 109 times higher.
β-sultam can be used as an irreversible active site-directed inhibitor of elastase, which is closely related to the treatment of diseases such as emphysema, cystic fibrosis and rheumatoid arthritis, in which the active site serine plays a therapeutic role through the cleavage of the S-N bond of β-sultam[81⇓~83]. β-sultam also acts as an inhibitor of β-lactamase and D, D-peptidase[84][85]. Therefore, chemists have made a series of explorations on the synthesis of β-sultam compounds. Sulfonyl chloride can undergo Sulfa-Staudinger reaction with imine to produce β-sultam.

3.1 Reaction of sulfonyl chloride with electron-rich imine

This type of reaction was first reported in 1970, when Iwanami et al. Reacted benzoylmethanesulfonyl chloride 96 with imine 97 in the presence of triethylamine to produce β-sultam 98 (Scheme 31)[86]. At that time, it was considered to be a synergistic cycloaddition mechanism of [2 + 2]. It is worth mentioning that the by-products of carbonyl olefin sulfone and imine [4 + 2] were also isolated at that time.
At the end of the 20th century, the Sulfa-Staudinger cyclization reaction of sulfonyl chloride with electron-rich nucleophilic chain imines was gradually developed[87⇓~89].
In 1997, Gordeev et al. Used chiral imines to synthesize optically active β-sultam compounds, which opened up a convenient synthesis of optically active β-sultam compounds[90].
In order to explore the mechanism of the reaction and the stereoselectivity of the product, our research group carried out the cyclization reaction of cyclic imine with sulfonyl chloride. The reaction of different cyclic imines with sulfonyl chloride was reported in 2011. Due to the weak nucleophilicity of sulfonyl carbanion, only N-sulfonylated products were obtained for most cyclic imines, and no β-sultam was formed[91]. However, this part of work lays a solid foundation for the exploration of the addition cyclization reaction of cyclic imines with sulfonyl chlorides.
The reaction of alkylsulfonyl chloride 1 with cyclic imine 99 with benzylidene structure was achieved in 2014 (Scheme 32)[92,93]. At room temperature, the stereoselective single trans-β-sultam 100 was obtained. Alkylsulfonyl chloride 1 reacts with chain imine 101 to give a mixture of cis-β-sultam cis-102 and trans-β-sultam trans-102. A stepwise reaction mechanism for the reaction of sulfonyl chloride with imine was proposed. N-Sulfonylimide salt 103 was first generated from the reaction of chain imine 101 with alkylsulfonyl chloride 1. Then a weak base (excess imine, pyridine, etc.) attacks the α-H of the sulfonyl group to produce an α-anion N-sulfonyl imine 104,104 resonates into a zwitterionic intermediate 105,105 undergoes direct conrotatory cyclization to give cis-102. If intermediate 105 undergoes an isomerization process to give intermediate 106, then intermediate 106 undergoes conrotatory cyclization to give trans-β-sultam trans-102. It not only reveals the nature of diastereoselectivity, but also provides a model to predict and control the diastereoselectivity of Sulfa-Staudinger cyclization.
The exploration of the reaction of sulfonyl chloride with imine was continued in 2015 (Scheme 33), and it was found that the selectivity of the Sulfa-Staudinger reaction of alkylsulfonyl chloride 1 and imine 101 was mainly controlled by the inherent properties of substrates such as the electronic effect of the α-substituent of sulfonyl chloride and the nucleophilicity of imine[94⇓~96]. By adjusting the substrate and temperature, the cis and trans β-sultam cis-102, trans-102 and the [2 + 2 + 2] product 107 of the reaction between one molecule of sulfonyl chloride and two molecules of imine were successfully obtained. The cyclization selectivity and stereochemistry of the cyclic imine Sulfa-Staudinger reaction were investigated using representative six- and seven-membered cyclic imines as probes. The results show that the selectivity and stereochemistry of the cyclization are closely related to the ring size of the cyclic imine. The steric hindrance and nucleophilicity of the cyclic imine not only control the selectivity of [2S + 2i] and [2S + 2i + 2i] cyclization in the reaction of weakly electron-withdrawing substituted sulfonyl chlorides, but also control the stereochemistry of [2S + 2i + 2i] cyclization in the reaction of strongly electron-donating substituted sulfonyl chlorides. When methanesulfonyl chloride was used to react with cyclic imine, it was found that the reaction temperature controlled the selectivity of the cyclization, resulting in [2S + 2i + 2i] cyclization products at low temperature and [2S + 2i] cyclization products at room temperature. The factors affecting the Sulfa-Staudinger reaction and the conditions controlling its cyclization selectivity and stereoselectivity were studied in detail, which provided a theoretical basis for the effective use of this kind of reaction in the future.
In 2017, Yang et al. Of our group studied and discussed the effect of o-nitro substrate on diastereoselectivity control in Sulfa-Staudinger cycloadduct[97]. Xu et al. Synthesized β-sultam with trifluoromethyl group, which has potential medicinal value[98].

3.2 Reaction of Sulfonyl Chloride with Electron Deficient Imine

In 2007, Peters et al. First reported the reaction of alkylsulfonyl chloride 1 with electron-deficient non-nucleophilic imine 109 (Scheme 34)[99]. The reaction was carried out at − 80 ° C with the addition of quinine ( NR 3 *) 108 as a catalyst and N, N-diisopropylethylamine as a base to afford chiral β-sultam 110 in high yield and high syn-diastereoselectivity. The mechanism of the reaction is as follows: the catalyst acts as a nucleophile to attack imine 109 to form amphoteric intermediate 111, then the anion of 111 attacks the nucleophile of sulfonyl chloride 1 to form intermediate 112, and finally N, N-diisopropylethylamine pulls out the hydrogen at the α-position of 112 sulfonyl to carry out the cyclization reaction. Derivatization of product 110 demonstrated the importance of the product, but unfortunately, only the electron-deficient imine substrate could be reacted.
In 2009, they realized the cyclization reaction of alkylsulfonyl chloride 1 with medium electron-deficient imine N-pyridinesulfonyl imine 115 using TMS quinine 114 as catalyst and Lewis acid Yb(OTf)3 as additive to produce trans-β-sultam 116 (Scheme 35)[100]. The effect of adding Yb(OTf)3 is to coordinate with pyridine and N on the imine group, which enhances the electron-deficient ability of imine 115, and also coordinates with the oxygen of sulfonyl chloride to control the stereoselectivity of the product. Using a variety of nucleophiles to open the ring of product 116, a variety of taurine derivatives can be generated, which proves the application value of the product again.

4 Reaction of sulfonyl chloride with aldehydes and ketones

β-sultone can be synthesized by the reaction of sulfonyl chloride with perhalogenated aldehydes and ketones. As early as 1967, Borrmann et al. Found that β-sultone derivative 118a could be obtained by [2 + 2] cyclization of methanesulfonyl chloride 1A with chloral 117A[101]. In 1969, Truce et al. Further studied the synthesis of β-sultone 118 from sulfonyl chloride 1 and perhalogenated aldehyde ketone 117 (Scheme 36)[102]. β-sultone has the structural characteristics of a tetrahedral intermediate, has good solubility in water, can act as a hydrogen bond acceptor, and is increasingly important in medicinal chemistry[103,104]. β-Sulfonolactone has been favored by chemists because of its important pharmaceutical effects and its nucleophilic ring-opening reaction to produce a variety of sulfonyl derivatives.
In 1970, Truce et al. Tried to use methanesulfonyl chloride 1A to react with partially halogenated aldehydes and ketones 119 with α-H to produce β-sultones, but only sulfonates 120 containing aldehydes, ketones, and enols were obtained (Scheme 36)[105].
In 2007, Peters et al. Reported the asymmetric catalytic reaction of alkylsulfonyl chloride 1 with chloral 117A (Scheme 37)[106]. Under the co-catalysis of organic base (DHQ)2PYR 121 and Lewis acid at -15 ℃, 1,2,2,6,6-pentamethylpiperidine (PMP) was used as base to give β-sultones 122 in moderate to excellent yields. In the reaction process, the sulfonyl chloride 1 is firstly attacked by a base to form the vinyl sulfone intermediate 4, and then the chiral catalyst 121 attacks the vinyl sulfone 4 to form the zwitterionic intermediate 123, and then the zwitterionic intermediate 123 attacks the electron-deficient aldehyde 117A, and the ring closure reaction occurs to obtain the target product 122. The reaction was proved to be carried out through the olefinic sulfone intermediate by deuteration experiment, and the product 122 was derivatized to obtain a large number of sulfonyl derivatives with pharmaceutical activity. The reaction has the advantages of low cost and high enantio- and diastereoselectivity. This is the first application of an olefinic sulfone intermediate in asymmetric synthesis and is of great significance. Unfortunately, the substrate is limited. In 2009, Peters et al. Carried out a large number of derivatization reactions of this kind of products, which confirmed the possibility of double electron-deficient system reaction and provided a new idea for the subsequent double electron-deficient system reaction[107].

5 Reaction of Sulfonyl Chloride with Other Unsaturated Compounds

In 2016, Zhou et al. Of our group realized the DABCO-promoted reaction of alkylsulfonyl chloride 1 with dialkyl azodicarboxylate 124 (Fig. 38)[108]. Dialkyl 1-chloroalkylsulfonylhydrazine-1,2-dicarboxylates 125 were produced in one step under the conditions of DABCO in moderate to excellent yields. In the reaction, DABCO reacts with sulfonyl chloride 1 to form vinyl sulfone 4, and attacks azo compound 124 nucleophilically to form amphoteric intermediate 126. Then the nitrogen anion of 126 attacks vinyl sulfone 4 to form intermediate 127, and then the intramolecular nucleophilic reaction proceeds to form intermediate 128. Finally, chloride ion attacks 128 to form target product 125. The reaction has the advantages of easy availability of raw materials and high atom economy.
In 2020, Cheng et al. Reported the reaction of alkylsulfonyl chloride 129 with 1,4-dipole pyridinethiol anion 130 (Scheme 39)[109]. The reaction was completed in 2 ~ 3 min at room temperature with DIPEA as base, and 1,9 a-dihydropyrido [2,1-c] [1,4] thiazine 131 was obtained using benzylsulfonyl chloride as substrate. If other alkylsulfonyl chlorides are used as substrates, 3H-1,2-dithiacyclopent-4-ene-2,2-dioxide 132 is formed. Sulfonyl chloride 129 first reacts with base to form vinyl sulfone 133, and the sulfur anion of 130 attacks vinyl sulfone 133 to form intermediate 134. If the reactant is benzylsulfonyl chloride, intermediate 134 undergoes ring closure via pathway a to form intermediate 135, and finally 135 undergoes SO2 to form product 131. If the reactant is other alkylsulfonyl chloride, intermediate 134 is cyclized via path B to form zwitterionic intermediate 136, and finally the carbanion attacks and pyridine leaves to form product 132.

6 Conclusion and prospect

So far, the reaction of sulfonyl chloride with unsaturated compounds has been explored for more than 60 years. Sulfonyl chloride has attracted much attention in recent years because of its low cost, easy preparation and high activity. The reactions of sulfonyl chloride with alkenes, alkynes, aromatic compounds, imines, aldehydes, azo and other unsaturated compounds have been reported, which can construct C — S bonds, N — S bonds, O — S bonds and C — C bonds, and synthesize structurally diverse four-membered heterocyclic compounds containing sulfonyl groups and compounds containing sulfonyl, sulfenyl and fluoroalkyl groups. Similar to the [2 + 2] cyclization reaction of ene sulfoxide and enone, the reaction of forming four-membered heterocycle is mostly the [2 + 2] cyclization reaction involving the ene sulfone intermediate[110][111⇓⇓⇓~115]. Among them, the research on sulfonyl chloride and carbon-carbon unsaturated compounds is the most extensive, including [2 + 2] cyclization reaction with electron-rich alkenes and alkynes and electron-deficient alkynes, free radical o-chlorosulfonylation, sulfonylation, hydrocarbon sulfurization and fluoroalkylation of alkenes and alkynes, etc. In the reaction of sulfonyl chloride with unsaturated compounds, sulfonyl chloride can be used as the donor of sulfonyl, sulfenyl and fluoroalkyl groups to produce compounds with different functional groups, most of which are the active structural units of drugs. With the development of photochemistry, there are more and more reports on the reaction of sulfonyl chloride with alkenes, alkynes and aromatic compounds.
Four-membered heterocyclic compounds are important structural units of pharmaceutical activity, especially sulfur-containing four-membered heterocyclic compounds[116⇓⇓~119]. β-Sultam and β-sultone have better stability than β-phosphinolactam and β-phosphinolactone[120][121]. However, the reaction of sulfonyl chloride with other unsaturated compounds such as imines, aldehydes and ketones has been studied relatively little. There are relatively few asymmetric catalytic reactions involving sulfonyl chloride and reactions between sulfonyl chloride and electron-deficient systems, which is believed to be the future direction of organic chemists. In this paper, the reactions of sulfonyl chloride with unsaturated systems are summarized, hoping to inspire scholars interested in this field and promote the development of this field.

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Funding

National Natural Science Foundation of China(21572017)

National Natural Science Foundation of China(21772010)

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