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Morpholine Ketene Aminal as Amide Enolate Surrogate in Iridium‐Catalyzed Asymmetric Allylic Alkylation
Author(s) -
Sempere Yeshua,
Alfke Jan L.,
Rössler Simon L.,
Carreira Erick M.
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.201903090
Subject(s) - morpholine , aminal , chemistry , ketene , allylic rearrangement , amide , iridium , alkylation , silanes , enantioselective synthesis , racemization , kinetic resolution , catalysis , medicinal chemistry , organic chemistry , combinatorial chemistry , silane
Morpholine ketene aminal is employed in iridium‐catalyzed asymmetric allylic alkylation reactions as a surrogate for amide enolates to prepare γ,δ‐unsaturated β‐substituted morpholine amides. Kinetic resolution or, alternatively, stereospecific substitution affords the corresponding products in high enantiomeric excess. The utility of the products generated by this method has been showcased by their further elaboration into amines, ketones, or acyl silanes. A putative catalytic intermediate (η 3 ‐allyl)iridium(III) with achiral P,Olefin‐ligand was synthetized and characterized for the first time.