Thiacrown Ether Technology in Lipase-Catalyzed Reaction:  Scope and Limitation for Preparing Optically Active 3-Hydroxyalkanenitriles and Application to Insect Pheromone Synthesis

Both reaction rate and enantioselectivity in Pseudomonas cepacia lipase (PCL)-catalyzed hydrolysis of 3-hydroxyalkanenitrile acetates were significantly changed by the addition of catalytic amounts of thiacrown ether (1,4,8,11-tetrathiacyclotetradecane). Although the reaction rate of various nitrile...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 1997-12, Vol.62 (26), p.9165-9172
Main Authors: Itoh, Toshiyuki, Mitsukura, Koichi, Kanphai, Wipa, Takagi, Yumiko, Kihara, Hiroshi, Tsukube, Hiroshi
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Both reaction rate and enantioselectivity in Pseudomonas cepacia lipase (PCL)-catalyzed hydrolysis of 3-hydroxyalkanenitrile acetates were significantly changed by the addition of catalytic amounts of thiacrown ether (1,4,8,11-tetrathiacyclotetradecane). Although the reaction rate of various nitriles was accelerated, the enantioselectivity greatly depended on the nature of the substrate. Among 10 substrates tested, thiacrown ether offered highest enantioselectivity in PCL-catalyzed hydrolysis of 1-(cyanomehtyl)propyl acetate. Forty or more times this crown ether, molarity based on the enzyme, was required to attain an acceptably high reaction rate and enantioselectivity. Applying this technology, we succeeded in synthesizing the optically pure attractant pheromone of ant Myrmica scabrinodis (A), (R)-3-octanol and its antipode of (S)-isomer in good overall yields.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo971288m