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Mechanism of Phosphine‐Catalyzed Allene Coupling Reactions: Advances in Theoretical Investigations
Author(s) -
Cui ChengXing,
Shan Chunhui,
Zhang YuPing,
Chen XiaoLan,
Qu LingBo,
Lan Yu
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201800146
Subject(s) - allene , phosphine , chemistry , regioselectivity , cycloaddition , protonation , electrophile , phosphonium , nucleophile , catalysis , coupling reaction , organocatalysis , photochemistry , combinatorial chemistry , organic chemistry , enantioselective synthesis , ion
Organocatalysis has emerged as an effective strategy for chemical synthesis. Within this area, phosphine‐catalyzed coupling reactions have attracted considerable attention because of their versatility and wide range of applications in the construction of new C−C bonds. Recently, various experimental studies on the phosphine‐catalyzed coupling reaction of allenes have been reported, and mechanistic and computational studies have also progressed considerably. As a nucleophile, phosphine can react with an allene to form a zwitterionic phosphoniopropenide intermediate. After stepwise cycloaddition and proton transfer, the phosphine catalyst can be regenerated by C−P bond cleavage. Alternatively, the zwitterionic phosphoniopropenide intermediate could also be protonated by a Brønsted acid to generate a phosphonium intermediate, which can be used to construct new C−C bonds by electrophilic addition. In this review, we have summarized details of mechanistic studies of phosphine‐catalyzed allene coupling reactions that follow these two reaction modes. In addition to detailing the reaction pathway, the regioselectivity and diastereoselectivity of the phosphine‐catalyzed allene coupling reaction are also discussed in this review.