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Practical and Broadly Applicable Catalytic Enantioselective Additions of Allyl‐B(pin) Compounds to Ketones and α‐Ketoesters
Author(s) -
Robbins Daniel W.,
Lee KyungA,
Silverio Daniel L.,
Volkov Alexey,
Torker Sebastian,
Hoveyda Amir H.
Publication year - 2016
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.201603894
Subject(s) - enantioselective synthesis , moiety , catalysis , chemistry , yield (engineering) , selectivity , enantiomer , combinatorial chemistry , medicinal chemistry , organic chemistry , materials science , metallurgy
A set of broadly applicable methods for efficient catalytic additions of easy‐to‐handle allyl‐B(pin) (pin=pinacolato) compounds to ketones and acyclic α‐ketoesters was developed. Accordingly, a large array of tertiary alcohols can be obtained in 60 to >98 % yield and up to 99:1 enantiomeric ratio. At the heart of this development is rational alteration of the structures of the small‐molecule aminophenol‐based catalysts. Notably, with ketones, increasing the size of a catalyst moiety (tBu to SiPh 3 ) results in much higher enantioselectivity. With α‐ketoesters, on the other hand, not only does the opposite hold true, since Me substitution leads to substantially higher enantioselectivity, but the sense of the selectivity is reversed as well.