Hemilabile Amidomonophosphine Ligand−Rhodium(I) Complex-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to Cycloalkenones
- 1 July 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (30) , 8932-8939
- https://doi.org/10.1021/ja0261933
Abstract
The asymmetric 1,4-addition reaction of arylboronic acids with cycloalkenones was catalyzed by 1 mol % of an amidomonophosphine−rhodium(I) catalyst in a 10:1 mixture of 1,4-dioxane and water at 100 °C, affording 3-arylcycloalkanones in reasonably high enantioselectivity and high yields. It was revealed by NMR, IR, and X-ray spectroscopies that this bidentate amidomonophosphine behaves as a hemilabile ligand that contains a hard donor site in addition to the soft donor in a molecule. Phosphorus atom strongly bonds to rhodium(I), and the amide carbonyl oxygen is coordinatively labile. The reaction efficacy of phenylboronic acid with cyclopent-2-en-1-one was significantly dependent on the possibility of coordination of the amide carbonyl oxygen to rhodium(I).Keywords
This publication has 21 references indexed in Scilit:
- Rhodium(I)-Catalyzed Asymmetric 1,4-Addition of Arylboronic Acids to α,β-Unsaturated AmidesThe Journal of Organic Chemistry, 2001
- Asymmetric Conjugate 1,4-Addition of Arylboronic Acids to α,β-Unsaturated Esters Catalyzed by Rhodium(I)/(S)-binapThe Journal of Organic Chemistry, 2000
- Asymmetric 1,4-addition of phenylboronic acid to 2-cyclohexenone catalyzed by Rh(I)/binap complexesChirality, 2000
- Chiral Monophosphines as Ligands for Asymmetric Organometallic Catalysis.CHEMICAL & PHARMACEUTICAL BULLETIN, 2000
- The Transition Metal Coordination Chemistry of Hemilabile LigandsPublished by Wiley ,1999
- Asymmetric Catalysis. Asymmetric Catalytic Intramolecular Hydroacylation of 4-Pentenals Using Chiral Rhodium Diphosphine CatalystsJournal of the American Chemical Society, 1994
- Asymmetric Synthesis and Highly Diastereoselective ortho‐Lithiation of Ferrocenyl Sulfoxides. Application to the Synthesis of Ferrocenyl Derivatives with Planar ChiralityAngewandte Chemie International Edition in English, 1993
- Asymmetric syntheses of 1,6-dialkyl-1,4-cyclohexadiene derivativesJournal of the American Chemical Society, 1991
- Aqua Ions of MolybdenumPublished by Wiley ,1985
- Asymmetric catalytic reduction with transition metal complexes. I. Catalytic system of rhodium(I) with (-)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, a new chiral diphosphineJournal of the American Chemical Society, 1972