Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
Org Lett. 2021 May 7;23(9):3615-3619. doi: 10.1021/acs.orglett.1c01004. Epub 2021 Apr 19.
Selective lithiation of arylsulfonylbicyclo[1.1.0]butanes at the bridgehead methine and addition to carbonyl compounds yield tertiary bicyclobutyl alcohols that form spiro[3.4]octanes and related heteroatom-containing spirocycles via an acid- or halogen-mediated semipinacol rearrangement. Further synthetic transformations at the carbonyl or arylsulfone positions, in general in high yield and good chemoselectivity, allow access to acetals, difluorides, amides, and methylenecyclobutene building blocks.
芳磺酰双环[1.1.0]丁烷在桥头亚甲基的选择性锂化反应，并与羰基化合物加成，生成叔双环丁基醇，通过酸或卤素介导的半频哪醇重排生成螺[3.4]辛烷和相关含杂原子的螺环。在羰基或芳磺酰基位置进一步进行合成转化，通常可以高产率和良好的化学选择性得到缩醛、二氟化物、酰胺和亚甲基环丁烯砌块。
