Asymmetric Hydrolytic Kinetic Resolution with Recyclable Macrocyclic CoIII-Salen Complexes: A Practical Strategy in the Preparation of (R)-Mexiletine and (S)-Propranolol

被引：25

作者：

Sadhukhan, Arghya ^{[1
]}

Khan, Noor-ul H. ^{[1
]}

Roy, Tamal ^{[1
]}

Kureshy, Rukhsana I. ^{[1
]}

Abdi, Sayed H. R. ^{[1
]}

Bajaj, Hari C. ^{[1
]}

机构：

[1] Council Sci & Ind Res CSIR, Discipline Inorgan Mat & Catalysis, Cent Salt & Marine Chem Res Inst CSMCRI, Bhavnagar 364021, Gujarat, India

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2012年 / 18卷 / 17期

关键词：

asymmetric synthesis; cobalt; kinetic resolution; macrocycles; salen ligands; CHIRAL CO(SALEN) COMPLEXES; HIGHLY ENANTIOSELECTIVE RESOLUTION; POLYMER BRUSH CATALYSTS; SOLVENT-FREE CONDITIONS; RING-OPENING REACTIONS; TERMINAL EPOXIDES; CO-SALEN; RACEMIC EPOXIDES; ENHANCED COOPERATIVITY; NITROALDOL REACTION;

D O I：

10.1002/chem.201103574

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A chiral cobalt(III) complex (1?e) was synthesized by the interaction of cobalt(II) acetate and ferrocenium hexafluorophosphate with a chiral dinuclear macrocyclic salen ligand that was derived from 1R,2R-(-)-1,2-diaminocyclohexane with trigol bis-aldehyde. A variety of epoxides and glycidyl ethers were suitable substrates for the reaction with water in the presence of chiral macrocyclic salen complex 1?e at room temperature to afford chiral epoxides and diols by hydrolytic kinetic resolution (HKR). Excellent yields (47?% with respect to the epoxides, 53?% with respect to the diols) and high enantioselectivity (ee>99?% for the epoxides, up to 96?% for the diols) were achieved in 2.516 h. The CoIII macrocyclic salen complex (1?e) maintained its performance on a multigram scale and was expediently recycled a number of times. We further extended our study of chiral epoxides that were synthesized by using HKR to the synthesis of chiral drug molecules (R)-mexiletine and (S)-propranolol.

引用

页码：5256 / 5260

页数：5

共 79 条

[1] Polymer-supported chiral Co(salen) complexes: Synthetic applications and mechanistic investigations in the hydrolytic kinetic resolution of terminal epoxides [J].