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Synthesis of Chiral 2‐Hydroxy‐1‐methylpropanoates by Rhodium‐Catalyzed Stereoselective Hydrogenation of α‐(Hydroxymethyl)‐acrylate Derivatives
Author(s) -
Holz Jens,
Schäffner Benjamin,
Zayas Odalys,
Spannenberg Anke,
Börner Armin
Publication year - 2008
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200800525
Subject(s) - chemistry , stereoselectivity , rhodium , kinetic resolution , catalysis , hydroxymethyl , organic chemistry , asymmetric hydrogenation , acrylate , enantioselective synthesis , stereochemistry , medicinal chemistry , copolymer , polymer
The synthesis of chiral 3‐hydroxy‐2‐methylpropanoic acid esters (e.g., “Roche ester” 3a ) based on the rhodium‐catalyzed stereoselective hydrogenation of Baylis–Hillman reaction products was investigated. Full conversions and enantioselectivities of up to 99% at a substrate/catalyst ratio of up to 500/1 were achieved by application of bisphospholanes of the cat AS ium M series as ancillary ligands. An interesting kinetic resolution was observed by the diastereoselective hydroxy‐directed hydrogenation of related racemic β‐branched precursors affording mainly anti ‐isomers with up to 96%ee.