向非对映从头合成羊毛甾烷：7,11-二去氧-Δ-羊毛甾酮 H 的构建。
Toward the Asymmetric de Novo Synthesis of Lanostanes: Construction of 7,11-Dideoxy-Δ-lucidadone H.
机构信息
Department of Chemistry, Dartmouth College, Burke Laboratory, Hanover, New Hampshire 03755, United States.
出版信息
J Org Chem. 2022 Nov 4;87(21):14975-14979. doi: 10.1021/acs.joc.2c02042. Epub 2022 Oct 7.
Abstract
Efforts to establish an asymmetric entry to hexanorlanostanes has resulted in a concise synthesis of 7,11-dideoxy-Δ-lucidadone H from epichlorohydrin. By exploiting metallacycle-mediated annulative cross-coupling (to establish a functionalized hydrindane) and stereoselective formation of the steroidal C9-C10 bond to establish a stereodefined 9-alkyl estrane, 14 subsequent steps have been established to generate a hexanorlanostane system. Key transformations include formal inversion of the C13 quaternary center, oxidative dearomatization/group-selective Wagner-Meerwein rearrangement, and Lewis acid mediated semi-Pinacol rearrangement.
摘要
努力建立一个非对映体进入六氢诺兰烷的方法，导致了从表氯醇简洁地合成了 7,11-去氧-Δ-卢卡达酮 H。通过利用金属环介导的环加成交叉偶联（建立一个功能化的茚满）和立体选择性形成甾体 C9-C10 键来建立一个立体定义的 9-烷基雌烷，已经确定了 14 个后续步骤来生成一个六氢诺兰烷系统。关键的转化包括 C13 叔碳原子的外消旋化、氧化去芳构化/基团选择性 Wagner-Meerwein 重排以及路易斯酸介导的半频哪醇重排。
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