Gan Xu-Cheng, Kotesova Simona, Castanedo Alberto, Green Samantha A, Møller Søren Lau Borcher, Shenvi Ryan A
Department of Chemistry, Scripps Research, La Jolla, California 92037, United States.
Graduate School of Chemical and Biological Sciences, Scripps Research, La Jolla, California 92037, United States.
J Am Chem Soc. 2023 Jul 26;145(29):15714-15720. doi: 10.1021/jacs.3c05428. Epub 2023 Jul 12.
Metal-hydride hydrogen atom transfer (MHAT) has emerged as a useful tool to form quaternary carbons from alkenes via hydrofunctionalization. Methods to date that cross-couple alkenes with sp partners rely on heterobimetallic catalysis to merge the two cycles. Here, we report an iron-only cross-coupling via putative MHAT/S2 steps that solves a key stereochemical problem in the synthesis of meroterpenoid eugenial C and obviates the need for nickel. The concise synthesis benefits from a conformationally locked disubstituted benzyl bromide and a locally sourced chiral pool terpene coupling partner.
金属氢化物氢原子转移（MHAT）已成为一种通过氢官能化由烯烃形成季碳的有用工具。迄今为止，使烯烃与sp伙伴交叉偶联的方法依赖于异双金属催化来合并两个循环。在此，我们报告了一种通过假定的MHAT/S2步骤进行的仅铁交叉偶联，该方法解决了半萜类化合物eugenial C合成中的一个关键立体化学问题，并且无需镍。简洁的合成得益于构象锁定的二取代苄基溴和本地来源的手性池萜烯偶联伙伴。
