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Highly Active and Enantioselective Rhodium‐Catalyzed Asymmetric 1,4‐Addition of Arylboronic Acid to α,β‐ Unsaturated Ketone by using Electron‐Poor MeO‐F 12 ‐BIPHEP
Author(s) -
Korenaga Toshinobu,
Maenishi Ryota,
Hayashi Keigo,
Sakai Takashi
Publication year - 2010
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.201000339
Subject(s) - chemistry , rhodium , catalysis , enantioselective synthesis , medicinal chemistry , phenylboronic acid , ketone , phosphine , organic chemistry
The asymmetric 1,4‐addition of phenylboronic acid to cyclohexenone were performed by using a low amount of rhodium/( R )‐(6,6′‐dimethoxybiphenyl‐2,2′‐diyl)bis[bis(3,4,5‐trifluorophenyl)phosphine] (MeO‐F 12 ‐BIPHEP) catalyst. Because the catalyst shows thermal resistance at 100 °C, up to 0.00025 mol% Rh catalyst showed good catalytic activity. The highest turnover frequency (TOF) and turnover number (TON) observed were 53,000 h −1 and 320,000, respectively. The enantioselectivities of the products were maintained at a high level of 98% ee in these reactions. The Eyring plots gave the following kinetic parameters (ΔΔ H ≠ =−4.0±0.1 kcal mol −1 and ΔΔ S ≠ =−1.3±0.3 cal mol −1 K −1 ), indicating that the entropy contribution is relatively small. Both the result and consideration of the transition state in the insertion step at the B3LYP/6‐31G(d) [LANL2DZ for rhodium] levels indicated that the less σ‐donating electron‐poor ( R )‐MeO‐F 12 ‐BIPHEP could be creating a rigid chiral environment around the rhodium catalyst even at high temperature.