Enantioselective synthesis of chiral sulfinates using chiral diamines

Nakamura, Shuichi; Tateyama, Moto-aki; Sugimoto, Hideki; Nakagawa, Masaya; Watanabe, Yoshihiko; Shibata, Norio; Toru, Takeshi

doi:10.1002/chir.20112

Cited by 13 publications

(4 citation statements)

References 42 publications

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“…We conclude that their reaction with sulfonyl chloride is slow but quite rapid with the corresponding sulfinyl chloride or other active sulfinylating agent formed in the reaction mixture. A chiral amine (entry 13) and chiral sulfoximine (entry 17) afforded reasonable yields of sulfinyl derivatives, but no diastereoselection was found . It is not immediately clear why pyrollidine (entry 8) and propargylamine (entry 16) reacted so poorly, but for the former, a considerable amount of sulfonamide was isolated.…”

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confidence: 99%

Expedient Synthesis of Sulfinamides from Sulfonyl Chlorides

et al. 2006

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Sulfinamides were synthesized from sulfonyl chlorides using a procedure involving the in situ reduction of sulfonyl chlorides. The reaction is broad in scope and easy to perform.Sulfinamides, especially chiral sulfinamides, play vital roles in the modern asymmetric chemistry. 1 Furthermore, sulfinamides can also act as N-sulfinyl protecting group in ease of removal under mild conditions. 2 Even though there are various procedures reported for the preparation of sulfinamides from sulfinic acids 3 , sulfinates 4 , sulfinyl chlorides 5 , disulfides 6 , and homolytic substitution at the sulfur atom 7 , these reactions often require two or more synthetic steps. A one-step process would be useful and increase the exploration of sulfinamide chemistry.Sulfinamides are useful compounds and can be transformed to a number of other important functional groups. 8 For example, they can be converted to sulfonimidoyl chlorides, whose chemistry is both interesting and useful. 9 We reported that benzothiazines can be prepared from N-aryl sulfinamides by oxidation with t-butyl hypochlorite and subsequent treatment with an alkene or alkyne in the presence of a Lewis acid. (Scheme 1). 10 The requisite sulfinamide was prepared from a sulfinyl choride in high yield. While sulfinyl chlorides are not exceptionally difficult to make, they are sensitive to hydrolysis and require preparation using noxious reagents such as thionyl chloride. We thought that a procedure to quickly access sulfinamides would be useful in both exploring sulfinamide chemistry and derivatives such as sulfonimidoyl chlorides.A number of years ago Sharpless 11 reported the synthesis of sulfinate esters from sulfonyl chlorides by a one-pot reductive esterification reaction using either phosphites as the reducing agent. Attempts to prepare sulfinamides by the Sharpless group were not successful. We thought however, that the modification of the synthesis of sulfinate esters introduced by Toru 12 , which used triarylphophines as the reductant, would be suitable for the synthesis of such compounds. This letter reports the realization of that idea.We began our studies by simply using Toru's procedure for sulfinate ester formation. 11 The results are summarized in Table 1. When a CH 2 Cl 2 solution of triphenylphosphine was added to the mixture of TsCl, TEA (10 equivalents) and BzNH 2 in CH 2 Cl 2 at 0 °C, only sulfonamide 6 and PPh 3 were detected by the NMR analysis of the crude mixture (entry 1). However, a small change in the addition sequence offered an encouraging result. When PPh 3 and benzylamine in CH 2 Cl 2 were added to a mixture of triethylamine and tosyl chloride, the desired HarmataM@Missouri.edu. NIH Public Access NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author Manuscript sulfinamide was isolated in 62% yield, (entry 2). Only a 14% yield of sulfinamide, accompanied by 40% sulfonamide, was isolated when the reaction was performed by the addition of PPh 3 to TsCl in CH 2 Cl 2 over 1 hour followed by addition of a mixture of BzNH 2 and T...

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Expedient Synthesis of Sulfinamides from Sulfonyl Chlorides

et al. 2006

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“…Chiral sulfinate are used as precursors of chiral sulfoxide by addition of an organometallic reagent (Andersen's method) . In 2005, Toru et al reported the addition of tert- butyl alcohol onto p -toluenesulfinyl chloride 488 in the presence of a stoichiometric amount of chiral diamines (Scheme ) . The best result was obtained with 2 equiv of diamine 492 , which produced the corresponding sulfinate 489 in 76% ee.…”

Section: 16 Addition To Sulfinyl Chloridementioning

confidence: 99%

Chiral Tertiary Diamines in Asymmetric Synthesis

2007

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“…For example, sulfinic esters were recently applied as efficient sulfenylating agents 7 and sulfonic esters as sulfonylating agents. 8 The classical methods for the synthesize of these classes of organosulfur compounds involve the reaction of sulf(o,i)nyl chlorides, 9,10 sulf(o,i)nic acids, 11,12 or sodium sulfonates 13 with alcohols. However, corrosion, instability, and/or difficult preparability of some of the sulf(i,o)nylating agents limited the utility of these methods.…”

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confidence: 99%