Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, United States.
J Org Chem. 2021 Nov 5;86(21):14290-14310. doi: 10.1021/acs.joc.1c02290. Epub 2021 Oct 21.
A method for the catalytic, enantioselective, carbosulfenylation of alkenes to construct 3,4-disubstituted chromans is described. Alkene activation proceeds through the intermediacy of enantioenriched, configurationally stable thiiranium ions generated from catalytic, Lewis base activation of an electrophilic sulfenylating agent. The transformation affords difficult-to-generate, enantioenriched, 3,4-disubstituted chromans in moderate to high yields and excellent enantioselectivities. A variety of substituents are compatible including electronically diverse functional groups as well as several functional handles such as aryl halides, esters, anilines, and phenols. The resulting thioether moiety is amenable to a number of functional group manipulations and transformations. Notably, the pendant sulfide was successfully cleaved to furnish a free thiol which readily provides access to most sulfur-containing functional groups which are present in natural products and pharmaceuticals.
描述了一种用于催化、对映选择性碳硫酯化烯烃以构建 3,4-二取代色满的方法。烯烃的活化是通过催化路易斯碱活化亲电亚磺酰化试剂生成的对映体富集、构型稳定的硫𬭩离子中间体进行的。该转化以中等至高产率和优异的对映选择性提供了难以生成的对映体富集的 3,4-二取代色满。各种取代基都相容，包括电子不同的官能团以及几种官能团如芳基卤化物、酯、苯胺和酚。所得的硫醚部分适合于许多官能团的操作和转化。值得注意的是，侧链上的硫醚很容易断裂，生成游离的硫醇，这为大多数天然产物和药物中存在的含硫官能团提供了便利的途径。
