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A 1,3,2‐Diazaphospholene‐Catalyzed Reductive Claisen Rearrangement
Author(s) -
Reed John H.,
Donets Pavel A.,
Miaskiewicz Solène,
Cramer Nicolai
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201904411
Subject(s) - stereocenter , catalysis , claisen rearrangement , enantioselective synthesis , chemistry , combinatorial chemistry , organic chemistry
1,3,2‐Diazaphospholenes (DAPs) are an emerging class of organic hydrides. In this work, we exploited them as efficient catalysts for very mild reductive Claisen rearrangements. The method is tolerant towards a wide variety of functional groups and operates at ambient temperature. Besides being enantiospecific for substrates with existing stereogenic centers, the diastereoselectivity can be switched by varying solvents and DAP catalysts. The reaction kinetics show direct rearrangements of O‐bound phospholene enolates and provide a proof‐of‐principle for catalytic enantioselective reactions.