（4 + 1）与（4 + 2）：环丁酮与三取代丙二烯通过碳 - 碳活化的催化分子内偶联反应
(4+1) vs (4+2): Catalytic Intramolecular Coupling between Cyclobutanones and Trisubstituted Allenes via C-C Activation.
作者信息
Zhou Xuan, Dong Guangbin
机构信息
Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2015 Oct 28;137(42):13715-21. doi: 10.1021/jacs.5b09799. Epub 2015 Oct 16.
Abstract
Herein we describe a rhodium-catalyzed (4+1) cyclization between cyclobutanones and allenes, which provides a distinct [4.2.1]-bicyclic skeleton containing two quaternary carbon centers. The reaction involves C-C activation of cyclobutanones and employs allenes as a one-carbon unit. A variety of functional groups can be tolerated, and a diverse range of polycyclic scaffolds can be accessed. Excellent enantioselectivity can be obtained, which is enabled by a TADDOL-derived phosphoramidite ligand. The bridged bicyclic products can be further functionalized or derivatized though simple transformations.
摘要
在此，我们描述了一种铑催化的环丁酮与丙二烯之间的(4+1)环化反应，该反应提供了一种独特的含有两个季碳中心的[4.2.1]双环骨架。该反应涉及环丁酮的C-C活化，并使用丙二烯作为一碳单元。可以耐受多种官能团，并且可以获得各种多环支架。通过TADDOL衍生的亚磷酰胺配体能够实现优异的对映选择性。通过简单的转化，桥连双环产物可以进一步官能化或衍生化。
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