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Kirmse–Doyle‐ and Stevens‐Type Rearrangements of Glutarate‐Derived Oxonium Ylides
Author(s) -
Skrobo Benedikt,
Schlörer Nils E.,
Neudörfl JörgM.,
Deska Jan
Publication year - 2018
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.201704624
Subject(s) - oxonium ion , desymmetrization , stereocenter , ylide , chemistry , tetrahydrofuran , allylic rearrangement , silyl ether , combinatorial chemistry , stereochemistry , organic chemistry , catalysis , enantioselective synthesis , silylation , ion , solvent
A novel chemoenzymatic synthetic cascade enables the preparation of densely decorated tetrahydrofuran building blocks. Here, the lipase‐catalyzed desymmetrization of 3‐alkoxyglutarates renders highly enantioenriched carboxylic acid intermediates, whose subsequent activation and oxonium ylide rearrangement by means of rhodium or copper complexes furnishes functionalized O‐heterocycles with excellent diastereoselectivity. The two‐step protocol offers a streamlined and flexible synthesis of tetrahydrofuranones bearing different benzylic, allylic or allenylic side chains with full control over multiple stereogenic centers.