铑和钪催化的五步多米诺序列法高官能化环戊烷的不对称合成
Asymmetric Synthesis of Highly Functionalized Cyclopentanes by a Rhodium- and Scandium-Catalyzed Five-Step Domino Sequence.
作者信息
Parr Brendan T, Li Zhanjie, Davies Huw M L
机构信息
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA, USA.
出版信息
Chem Sci. 2011 Jan 1;2(12):2378-2382. doi: 10.1039/C1SC00434D. Epub 2011 Sep 2.
Abstract
A domino sequence has been developed between vinyldiazoacetates and racemic allyl alcohols, involving five distinct steps. The sequence generates highly functionalized cyclopentanes with four new stereogenic centers as single diastereomers in 64-92% ee. The first step is a rhodium-catalyzed oxygen ylide formation, which is then followed by a [2,3]-sigmatropic rearrangement, an oxy-Cope rearrangement, a keto/enol tautomerization, and then finally a carbonyl ene reaction. With appropriate substrates, a further silyl deprotection and a 6-exo-trig cyclization can be added to the domino process.
摘要
已开发出一种在乙烯基重氮乙酸酯和外消旋烯丙醇之间的多米诺反应序列，该序列包含五个不同步骤。该序列能生成具有四个新立体中心的高度官能化环戊烷，以单一非对映异构体形式存在，对映体过量值为64 - 92%。第一步是铑催化的氧叶立德形成，随后是[2,3]-σ迁移重排、氧杂-Cope重排、酮/烯醇互变异构，最后是羰基烯反应。使用合适的底物时，可在多米诺反应过程中进一步添加硅基脱保护和6-外向-三环化反应。
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