β-Hydroxycarboxylic Acids from Simple Ketones by Carboxylation and Asymmetric Hydrogenation

We present a new asymmetric synthesis of β‐hydroxycarboxylic acids from ketones, performed by carboxylation using CO2 followed by asymmetric hydrogenation. First, the carboxylation of ketones gives β‐ketocarboxylic acids. The effects of temperature, reaction time, and amount of 1,8‐diazabicyclo[5.4....

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Bibliographic Details
Published in:	Advanced synthesis & catalysis Vol. 350; no. 18; pp. 2947 - 2958
Main Authors:	Flowers, Brendan J., Gautreau-Service, Robyn, Jessop, Philip G.
Format:	Journal Article
Language:	English
Published:	Weinheim WILEY-VCH Verlag 01-12-2008 WILEY‐VCH Verlag
Subjects:	asymmetric catalysis carbon dioxide fixation carboxylation hydrogenation ketones
Online Access:	Get full text
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Summary:	We present a new asymmetric synthesis of β‐hydroxycarboxylic acids from ketones, performed by carboxylation using CO2 followed by asymmetric hydrogenation. First, the carboxylation of ketones gives β‐ketocarboxylic acids. The effects of temperature, reaction time, and amount of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) promoter on the carboxylation were investigated. The DBU can be recycled. For the second step, the asymmetric hydrogenation of these β‐ketocarboxylic acids, we determined the effect of solvent choice, H2 pressure, and substrate substitution. Hydrogenation yield and enantioselectivity are solvent‐dependent, and the mechanism could proceed through hydrogenation of either the enol or the keto forms of the bound substrate. This synthesis is industrially advantageous due to the limited number of reactants required, their low‐cost, and the potential for recycling unused materials.
Bibliography:	NSERC Discovery grant program Robert Samuel McLaughlin Fellowship Canada Research Chairs program ark:/67375/WNG-LZPG7BPS-W istex:BE50182D41A6D47BDD785810199FCEE9A6B3E716 ArticleID:ADSC200800516 ObjectType-Article-2 SourceType-Scholarly Journals-1 ObjectType-Feature-1 content type line 23
ISSN:	1615-4150 1615-4169
DOI:	10.1002/adsc.200800516