Enantio‐ and Diastereoselective, Lewis Base Catalyzed, Cascade Sulfenoacetalization of Alkenyl Aldehydes

A catalytic, enantio‐, and diastereoselective formation of sulfenyl acetals bearing multiple stereogenic centers is reported. Alkenyl aldehydes undergo a chiral thiiranium ion initiated cascade starting with intramolecular capture by a formyl group and termination by capture with HFIP solvent. This...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-09, Vol.58 (36), p.12486-12490
Main Authors: Matviitsuk, Anastassia, Denmark, Scott E.
Format: Article
Language:English
Subjects:
Acetals
Aldehydes
carbonyl nucleophiles
Catalysis
isochromans
Lewis base
Lewis base catalysis
Stereoselectivity
sulfenoacetalization
thiiranium ions
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Summary:A catalytic, enantio‐, and diastereoselective formation of sulfenyl acetals bearing multiple stereogenic centers is reported. Alkenyl aldehydes undergo a chiral thiiranium ion initiated cascade starting with intramolecular capture by a formyl group and termination by capture with HFIP solvent. This method provides a one‐pot synthesis of dihydropyran and 1,3‐disubstituted isochroman acetals in good to excellent yield and with high levels of diastereo‐ (up to >99:1 dr) and enantiocontrol (up to 99:1 er). Thiiranium ion intermediates: A diastereo‐ and enantioselective Lewis base catalyzed sulfenoacetalization of alkenyl aldehydes is reported. A chiral thiiranium ion initiated cascade starts with intramolecular capture by a formyl group followed by capture with HFIP solvent. The resulting dihydropyran and 1,3‐disubstituted isochroman acetals are formed in good to excellent yield and with high levels of diastereo‐ and enantiocontrol.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201906535