Enantio- and Diastereoselective 1,2-Additions to α-Ketoesters with Diborylmethane and Substituted 1,1-Diborylalkanes

The catalytic enantioselective synthesis of boronate‐substituted tertiary alcohols through additions of diborylmethane and substituted 1,1‐diborylalkanes to α‐ketoesters is reported. The reactions are catalyzed by readily available chiral phosphine/copper(I) complexes and produce β‐hydroxyboronates...

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Published in:Angewandte Chemie (International ed.) 2016-07, Vol.55 (31), p.9065-9069
Main Authors: Murray, Stephanie A., Green, Jacob C., Tailor, Sanita B., Meek, Simon J.
Format: Article
Language:English
Subjects:
Alcohols - chemical synthesis
Alcohols - chemistry
Alkanes - chemistry
asymmetric catalysis
boron
Boron Compounds - chemistry
copper
enantioselectivity
Esters - chemistry
Ketones - chemistry
Methane - chemistry
Molecular Structure
reaction mechanisms
Stereoisomerism
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Summary:The catalytic enantioselective synthesis of boronate‐substituted tertiary alcohols through additions of diborylmethane and substituted 1,1‐diborylalkanes to α‐ketoesters is reported. The reactions are catalyzed by readily available chiral phosphine/copper(I) complexes and produce β‐hydroxyboronates containing up to two contiguous stereogenic centers in up to 99:1 e.r. and greater than 20:1 d.r. The utility of the organoboron products is demonstrated through several chemoselective functionalizations. Evidence indicates the reactions occur via an enantioenriched α‐boryl‐copper‐alkyl intermediate. Catalytic enantioselective synthesis of boronate‐substituted tertiary alcohols is possible through the title reaction. The reactions are catalyzed by chiral phosphine/copper(I) complexes and produce β‐hydroxyboronates containing up to two contiguous stereogenic centers. The utility of the organoboron products is demonstrated through several chemoselective functionalizations. pin=pinacolato, TMS=trimethylsilyl.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201603465