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Synfacts 2014; 10(1): 0059
DOI: 10.1055/s-0033-1340451
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Ring Opening of Azabicyclic Alkenes Co-Catalyzed by Palladium and Copper

Contributor(s):
Mark Lautens
,
Christine M. Le
Fan B, * Li S, Chen H, Lu Z, Liu S, Yang Q, Yu L, Xu J, Zhou Y, Wang J. * Yunnan University of Nationalities, Kunming and South University of Science and Technology of China, Shenzhen, P. R. of China
Palladium/Copper Complexes Co-Catalyzed Highly Enantioselective Ring Opening Reaction of Azabenzonorbornadienes with Terminal Alkynes.

Adv. Synth. Catal. 2013;
355: 2827-2832
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Publication History

Publication Date:
13 December 2013 (online)

 
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Key words

desymmetrization - asymmetric ring opening - palladium - copper

Significance

The ring opening of strained meso-heterobicyclic alkenes with different nucleophiles serves as a useful strategy for setting multiple stereocenters in a single transformation. Previous methods for this particular ring opening were limited to the use of bulky terminal acetylenes. Here, the authors report the development of a palladium and copper co-catalyzed system that exhibits broad substrate scope.


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Comment

The authors propose that the copper(I) catalyst plays two distinct roles in the mechanism: (1) Copper facilitates transmetalation of the acetylene to palladium via the copper acetylide; (2) Copper behaves as a Lewis acid to activate the azabicyclic alkene. In addition to demonstrating wide functional group tolerance, the yields and enantioselectivities observed are excellent across the series of substrates tested.


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