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Metallophosphite‐Induced Nucleophilic Acylation of α,β‐Unsaturated Amides: Facilitated Catalysis by a Diastereoselective Retro [1,4] Brook Rearrangement
Author(s) -
Nahm Mary R.,
Linghu Xin,
Potnick Justin R.,
Yates Christopher M.,
White Peter S.,
Johnson Jeffrey S.
Publication year - 2005
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.200462795
Subject(s) - chemistry , nucleophile , acylation , umpolung , allylic rearrangement , alkene , nucleophilic addition , aldehyde , carbene , organocatalysis , medicinal chemistry , enantioselective synthesis , catalysis , organic chemistry
Intermolecular alkene acylation reactions between acyl silanes and α,β‐unsaturated amides with metallophosphite catalysis afford α‐silyl‐γ‐ketoamides with high diastereoselectivities (see scheme). These can be converted into the corresponding γ‐ketoamides and α‐bromo‐γ‐ketoamides. Asymmetric catalysis of the acylation delivers the γ‐ketoamide in the highest enantioselectivity yet reported for an intermolecular Stetter‐type reaction.