Synthesis of Quaternary Carbon Stereocenters by Copper-Catalyzed Asymmetric Allylic Substitution of Allyl Phosphates with Arylboronates

详细信息    查看全文

• 作者：Momotaro Takeda ; Keishi Takatsu ; Ryo Shintani ; Tamio Hayashi
• 刊名：Journal of Organic Chemistry
• 出版年：2014
• 出版时间：March 21, 2014
• 年：2014
• 卷：79
• 期：6
• 页码：2354-2367
• 全文大小：650K
• 年卷期：v.79,no.6(March 21, 2014)
• ISSN：1520-6904

文摘

A copper-catalyzed asymmetric allylic substitution of 纬,纬-disubstituted allyl phosphates with arylboronates has been developed for the construction of quaternary stereocenters. High regio- and enantioselectivities have been achieved by employing a hydroxy-bearing chiral N-heterocyclic carbene ligand, and both E and Z substrates provide the same enantiomer as the major product. The mechanistic aspect of this catalysis has also been investigated to find that a 1:1 copper/ligand complex is most likely responsible for the present asymmetric catalysis, and the reaction proceeds with almost perfect 1,3-anti stereochemistry with respect to the allylic electrophile.