Kinetic and Dynamic Kinetic Resolution of Secondary Alcohols with Ionic-Surfactant-Coated Burkholderia cepacia Lipase: Substrate Scope and Enantioselectivity

• Published in: Journal of organic chemistry 2013-03, Vol.78 (6), p.2571-2578
• Main Authors: Kim, Cheolwoo, Lee, Jusuk, Cho, Jeonghun, Oh, Yeonock, Choi, Yoon Kyung, Choi, Eunjeong, Park, Jaiwook, Kim, Mahn-Joo
• Format: Article
• Language: English
• Subjects: Alcohols - chemistry; Alkynes; Burkholderia cepacia - chemistry; Burkholderia cepacia - enzymology; Kinetics; Lipase - chemistry; Molecular Dynamics Simulation; Propanols; Stereoisomerism; Surface-Active Agents - chemistry
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo3027627

Forty-four different secondary alcohols, which can be classified into several types (II-IX), were tested as the substrates of ionic surfactant-coated Burkholderia cepacia lipase (ISCBCL) to see its substrate scope and enantioselectivity in kinetic and dynamic kinetic resolution (KR and DKR). They include 6 boron-containing alcohols, 24 chiral propargyl alcohols, and 14 diarylmethanols. The results from the studies on KR indicate that ISCBCL accepted most of them with high enantioselectivity at ambient temperature and with useful to high enantioselectivity at elevated temperatures. In particular, ISCBCL displayed high enantioselectivity toward sterically demanding secondary alcohols (types VIII and IX) which have two bulky substituents at the hydroxymethine center. DKR reactions were performed by the combination of ISCBCL with a ruthenium-based racemization catalyst at 25–60 °C. Forty-one secondary alcohols were tested for DKR. About half of them were transformed into their acetates of high enantiopurity (>90% ee) with good yields (>80%). It is concluded that ISCBCL appears to be a superb enzyme for the KR and DKR of secondary alcohols.