使用联合烯丙基烷基化/Stork-Danheiser 方法合成对映体富集的γ-季碳环庚烯酮：单环、双环和三环系统的制备。
Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork-Danheiser approach: preparation of mono-, bi-, and tricyclic systems.
机构信息
The Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, California Institute of Technology, Division of Chemistry and Chemical Engineering, Mail Code 101-20, Pasadena, CA 91125, USA.
出版信息
Org Biomol Chem. 2012 Jan 7;10(1):56-9. doi: 10.1039/c1ob06189e. Epub 2011 Oct 19.
Abstract
A general method for the synthesis of β-substituted and unsubstituted cycloheptenones bearing enantioenriched all-carbon γ-quaternary stereocenters is reported. Hydride or organometallic addition to a seven-membered ring vinylogous ester followed by finely tuned quenching parameters achieves elimination to the corresponding cycloheptenone. The resulting enones are elaborated to bi- and tricyclic compounds with potential for the preparation of non-natural analogs and whose structures are embedded in a number of cycloheptanoid natural products.
摘要
本文报道了一种通用的方法，用于合成具有手性全碳γ-季碳中心的β-取代和未取代的环庚烯酮。通过对七元环烯酮酯进行氢化物或有机金属加成，然后精细调整淬灭参数，实现了相应的环庚烯酮的消除反应。所得的烯酮被进一步转化为双环和三环化合物，具有制备非天然类似物的潜力，其结构嵌入在许多环庚烷类天然产物中。
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