Maiti Mamata, Roy Subha, Maji Biplab
Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata, Mohanpur 741246, India.
Org Lett. 2025 Jun 27;27(25):6670-6675. doi: 10.1021/acs.orglett.5c01695. Epub 2025 Jun 16.
Herein, we report the cobalt-catalyzed asymmetric ene-yne reductive coupling of internal alkynes and unactivated cyclobutenes. The reaction produced densely functionalized chiral vinyl cyclobutanes in up to 92% yields with excellent absolute and relative stereocontrol (>99% ee, >20:1 dr, and >20:1 /), and high >20:1 regioselectivity. The scaled-up reaction and the postsynthetic derivatizations further elucidated the efficiency of the designed protocol. The preliminary mechanistic investigations suggested the involvement of zinc-mediated low-valent cobalt(I) complex generation, oxidative ene-yne cyclization, and protonation as the key mechanistic steps.
在此，我们报道了钴催化的内炔烃与未活化环丁烯的不对称烯炔还原偶联反应。该反应以高达92%的产率生成了高度官能化的手性乙烯基环丁烷，具有出色的绝对和相对立体控制（>99% ee，>20:1 dr，以及>20:1 /），并且区域选择性高达>20:1。放大反应和合成后衍生化进一步阐明了所设计方案的效率。初步机理研究表明，锌介导的低价钴（I）配合物生成、氧化烯炔环化和质子化是关键的机理步骤。
