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Novel Organocatalytic Activation of Unmodified Morita–Baylis–Hillman Alcohols for the Synthesis of Bicyclic α‐Alkylidene‐Ketones
Author(s) -
Stiller Julian,
Kowalczyk Dorota,
Jiang Hao,
Jørgensen Karl Anker,
Albrecht Łukasz
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404468
Subject(s) - stereocenter , iminium , bicyclic molecule , chemistry , reactivity (psychology) , organocatalysis , stereoselectivity , enamine , enantioselective synthesis , stereochemistry , catalysis , combinatorial chemistry , organic chemistry , medicine , alternative medicine , pathology
The organocatalytic activation of Morita–Baylis–Hillman alcohols via H‐bonding‐iminium‐ion formation is demonstrated for the first time. This activation strategy enables the Morita‐Baylis–Hillman alcohols to undergo a formal S N 2′ reaction. In combination with the well‐established enamine reactivity, this creates a new reactivity pattern. The application of this new activation mode for the synthesis of bicyclic α‐alkylidene‐ketones is demonstrated. The developed reaction sequence proceeds efficiently affording nature‐inspired target products with four contiguous stereogenic centers in a highly stereoselective manner.