Asymmetric Synthesis of Highly Functionalized Cyclopentanes by a Rhodium- and Scandium-Catalyzed Five-Step Domino Sequence.
Asymmetric Synthesis of Highly Functionalized Cyclopentanes by a Rhodium- and Scandium-Catalyzed Five-Step Domino Sequence.
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DOI：
10.1039/c1sc00434d
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发表时间：
2011-01-01
期刊：
影响因子：
8.4
通讯作者：
Davies HM
中科院分区：
文献类型：
--
作者：
Parr BT;Li Z;Davies HM
重氮乙酸乙烯酯和外消旋烯丙醇之间的多米诺序列已经开发，涉及五个不同的步骤。该序列产生高度官能化的环戊烷与四个新的立体异构中心作为单一的非对映异构体在64- 92%ee。第一步是铑催化的氧叶立德形成，然后由[2，3]-sigmatropic重排，oxy-Cope重排，酮/烯醇互变异构化，然后最后羰基烯反应。在适当的底物下，可以将进一步的甲硅烷基脱保护和6-外-二环化添加到多米诺过程中。
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.