Diastereo- and Enantioselective Hydrogenative Aldol Coupling of Vinyl Ketones: Design of Effective Monodentate TADDOL-Like Phosphonite Ligands
- 12 February 2008
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 130 (9) , 2746-2747
- https://doi.org/10.1021/ja710862u
Abstract
We report the first enantioselective reductive aldol couplings of vinyl ketones, which were achieved through the design of a novel monodentate TADDOL-like phosphonite ligand. Specifically, hydrogenation of commercially available methyl vinyl ketone (MVK) or ethyl vinyl ketone (EVK) in the presence of aldehydes 1a−7a using cationic rhodium catalysts modified by chiral TADDOL-like phosphonite ligands AP-I and AP-IV produces aldol adducts 1b−7b and 1c−7c with excellent control of relative and absolute stereochemistry. The absolute stereochemical assignments of the aldol adducts are made in analogy to that determined for the 5-bromophthalimido derivative of aldol adduct 1b and the 2-bromo-5-nitrobenzoate of 3b, which were established by single-crystal X-ray diffraction analysis using the anomalous dispersion method.Keywords
This publication has 35 references indexed in Scilit:
- Intermolecular Asymmetric Reductive Aldol Reaction of Ketones as Acceptors Promoted by Chiral Rh(Phebox) CatalystOrganic Letters, 2007
- A Simple Primary−Tertiary Diamine−Brønsted Acid Catalyst for Asymmetric Direct Aldol Reactions of Linear Aliphatic KetonesJournal of the American Chemical Society, 2007
- Hydrogen-Mediated C−C Bond Formation: A Broad New Concept in Catalytic C−C Coupling1The Journal of Organic Chemistry, 2006
- Dramatic Ligand Effect in Catalytic Asymmetric Reductive Aldol Reaction of Allenic Esters to KetonesJournal of the American Chemical Society, 2006
- Highly Diastereo‐ and Enantioselective Copper‐Catalyzed Domino Reduction/Aldol Reaction of Ketones with Methyl AcrylateAngewandte Chemie International Edition in English, 2006
- Rhodium-Catalyzed Reductive Aldol Reactions Using Aldehydes as the Stoichiometric ReductantsJournal of the American Chemical Society, 2005
- High Performance of Rh(Phebox) Catalysts in Asymmetric Reductive Aldol Reaction: High Anti-SelectivityJournal of the American Chemical Society, 2005
- Catalytic Generation of Indium Hydride in a Highly Diastereoselective Reductive Aldol ReactionAngewandte Chemie International Edition in English, 2004
- Metallo-Aldehyde Enolates via Enal Hydrogenation: Catalytic Cross Aldolization with Glyoxal Partners As Applied to the Synthesis of 3,5-Disubstituted PyridazinesThe Journal of Organic Chemistry, 2004
- Direct Catalytic Asymmetric Aldol ReactionJournal of the American Chemical Society, 1999