345-91-5Relevant articles and documents
Electronic Effect-Guided Rational Design of Candida antarctica Lipase B for Kinetic Resolution Towards Diarylmethanols
Li, Dan-Yang,Lou, Yu-Jiao,Xu, Jian,Chen, Xiao-Yang,Lin, Xian-Fu,Wu, Qi
supporting information, p. 1867 - 1872 (2021/02/12)
Herein, we developed an electronic effect-guided rational design strategy to enhance the enantioselectivity of Candida antarctica lipase B (CALB) mutants towards bulky pyridyl(phenyl)methanols. Compared to W104A mutant previously reported with reversed S-stereoselectivity toward sec-alcohols, three mutants (W104C, W104S and W104T) displayed significant improvement of S-enantioselectivity in the kinetic resolution (KR) of various phenyl pyridyl methyl acetates due to the increased electronic effects between pyridyl and polar residues. The electronic effects were also observed when mutating other residues surrounding the stereospecificity pocket of CALB, such as T42A, S47A, A281S or A281C, and can be used to manipulate the stereoselectivity. A series of bulky pyridyl(phenyl) methanols, including S-(4-chlorophenyl)(pyridin-2-yl) methanol (S-CPMA), the intermediate of bepotastine, were obtained in good yields and ee values. (Figure presented.).
Arylation of carbonyl compounds catalyzed by rhodium and iridium 1,3-R 2-tetrahydropyrimidin-2-ylidenes: Structure-reactivity correlations
Imlinger, Nicolas,Mayr, Monika,Wang, Dongren,Wurst, Klaus,Buchmeiser, Michael R.
, p. 1836 - 1843 (2007/10/03)
Six different well-defined rhodium and iridium N-heterocyclic carbene complexes, i.e., RhCl-(1,3-dimesityltetrahydropyrimidin-2-ylidene)(COD) (1), RhBr(1,3-dimesityltetrahydropyrimidin-2-ylidene)-(COD) (2), RhCl[1,3-di(2- propyl)tetrahydropyrimidin-2-ylidene](COD) (3), IrCl(1,3- dimesityltetrahydropyrimidin-2-ylidene)(COD) (4), Rh(CF3COO) (1,3-dimesityltetrahydropyrimidin-2-ylidene)(COD) (5), and IrBr[1,3-di(2-propyl) tetrahydropyrimidin-2-ylidene](COD) (6) (COD = 1,5-cyclooctadiene, mesityl = 2,4,6-trimethylphenyl) have been used as catalysts for the arylation of aldehydes and α,β-unsaturated ketones using different arylboronic acids. Compounds 1-4 and 6 were prepared by reaction of [RhCl(COD)]2 and [IrCl(COD)]2, respectively, with a base and the corresponding 1,3-R2-tetrahydropyrimidinium salt. Compound 5 was prepared by reaction of 1.0 equivalents of CF3COOAg with 1. The use of an excess of CF3COOAg resulted in the replacement of Rh(I) by Ag(I) and yielded Ag(1,3-dimesityltetrahydropyrimidin-2-ylidene)+Rh 2(CF3COO)3(COD)- (8). Compounds 4 and 8 were characterized by X-ray analysis. The activity of the rhodium complexes increased in the order 5 > 3 > 1 > 2, indicating the necessity of strongly electron-withdrawing groups at the metal centers, thus increasing their nucleophilicity. In due consequence, the softer iridium complexes 4 and 6 exhibited significantly reduced catalytic activity albeit with enhanced selectivity. The syntheses of the metal complexes as well as a detailed study on their reactivity in the arylation of carbonyl compounds using equimolar amounts of arylboronic acid and carbonyl compound in the presence of 0.08-1 mol % catalyst are presented.