21503-12-8Relevant articles and documents
One-pot kinetic resolution-Mitsunobu reaction to access optically pure compounds, using silver salts in the substitution protocol
Raval, Hiten B.,Bedekar, Ashutosh V.
, p. 21238 - 21243 (2020/12/31)
A practical method is developed to access chiral arylalkyl carbinols with a high yield from racemic alcohols. A one-pot enzyme mediated Kinetic Resolution followed by Mitsunobu esterification of the unreacted enantiomer of alcohol with metal acetate results in a nearly complete formation of chiral acetate. Substitution with AgOAc was found to be the most efficient, and the use of sub stoichiometric amounts of AgNO3 and excess of NaOAc affords comparable results; the protocol was further extended to introduce azide as a nucleophile.
CO2-expanded bio-based liquids as novel solvents for enantioselective biocatalysis
Hoang, Hai Nam,Nagashima, Yoshihiro,Mori, Shuichi,Kagechika, Hiroyuki,Matsuda, Tomoko
, p. 2984 - 2989 (2017/04/26)
For the first time, CO2-expanded bio-based liquids were reported as novel and sustainable solvents for biocatalysis. Herein, it was found that by expansion with CO2, 2-methyltetrahydrofuran (MeTHF), and other bio-based liquids, which were not favorable solvents for immobilized Candida antarctica lipase B (Novozym 435) catalyzed transesterification, were tuned into excellent reaction media. Especially, for the kinetic resolution of challenging bulky secondary substrates such as rac-1-adamantylethanol, the lipase displayed very high activity with excellent enantioselectivity (E value > 200) in CO2-expanded MeTHF (MeTHF concentration 10% v/v, 6 MPa), whereas there was almost no activity observed in conventional organic solvents.
Ligand effect in racemization and dynamic kinetic resolution of alcohols: Mechanism on cymene ruthenium complexes
Cao, Hui,Cai, Li-Hua,Wang, Chen-Xi,Zhu, Xiao-Han,Li, Zhi-Ming,Hou, Xiu-Feng
, p. 60 - 66 (2014/12/11)
A family of ruthenium complexes with different ligands was utilized in racemization of (R)-1-phenylethanol to investigate the potential influence of the ligands coordinated to the ruthenium center. Kinetic experiments showed that 16-electron cymene ruthenium complex with two chloro-bridge bonds and 18-electron ones with easily dissociative ligands are highly active for catalytic racemization of alcohols. Possible racemization mechanism for cymene ruthenium complexes was then proposed. Computational analysis of dissociation energy barrier, NBO analysis and reaction potential energy surface suggest that ligand-dissociation process is the vital step of the racemization catalyzed by cymene ruthenium complexes. Thereafter, these complexes were applied in the DKR of secondary alcohols to verify their efficiency and applicability.