stereo-selective synthesis of 5-norbornene-2-exo-carboxylic acid—rapid isomerization and kinetically selective hydrolysisstereo-selective合成5-norbornene-2-exo-carboxylic acid-rapid异构化活动选择性水解.pdf

International Journal of Organic Chemistry, 2012, 2, 26-30 / 10.4236/ijoc.2012.21005 Published Online March 2012 (http://www.SciRP.org/journal/ijoc) Stereo-Selective Synthesis of 5-Norbornene-2-exo-carboxylic Acid—Rapid Isomerization and Kinetically Selective Hydrolysis Miki Kanao, Atsushi Otake, Kousuke Tsuchiya, Kenji Ogino Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Tokyo, Japan Email: kogino@cc.tuat.ac.jp Received January 11, 2012; revised February 16, 2012; accepted February 25, 2012 ABSTRACT Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomeriza- tion was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed. Keywords: Stereo-Selective Synthesis; 2-Substituted Norbornene; Isomerization; Kinetically Selective Hydrolysis 1. Introduction Some of exo-selective syntheses of norbornene deriva-