Chiral dioxomolybdenum(VI) complexes for enantioselective alkene epoxidation

被引:66
作者
Gonçalves, IS
Santos, AM
Romao, CC
Lopes, AD
Rodríguez-Borges, JE
Pillinger, M
Ferreira, P
Rocha, J
Kühn, FE
机构
[1] Univ Nova Lisboa, Inst Tecnol Quim & Biol, EAN, P-2781901 Oeiras, Portugal
[2] Univ Aveiro, Dept Quim, P-3810193 Aveiro, Portugal
[3] Tech Univ Munich, Inst Anorgan Chem, D-85747 Garching, Germany
[4] Univ Santiago de Compostela, Fac Farm, Dept Quim Organ, E-15706 Santiago, Spain
关键词
molybdenum complexes; chiral ligands; enantioselective epoxidations; heterogeneous catalysis; mesoporous materials; supported catalysts;
D O I
10.1016/S0022-328X(00)00790-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Chiral dioxomolybdenum(M) complexes of the type MoO2Cl2(L*) (L* = oxime), MoO2(THF)(2)L* (L* = cis-p-menthane-3,8-diol) and MoO2Cl(THF)L* (L* = 8-phenylthioneomenthol and 8-phenylthioisoneomenthol) have been prepared in good yields by reacting MoO2Cl2(THF)(2) with the appropriate chiral organic bidentate O,O-, O,N- and O,S-ligands. The complexes were characterised by solution NMR (H-1, C-13, Mo-95) and IR spectroscopy as well as elementary analysis, and were evaluated as catalysts in solution for the asymmetric epoxidation of cis-beta -methylstyrene by tert-butylhydroperoxide (TBHP). The cis-diol complex shows high catalytic activity and enantiomeric excesses of up to 25%. An attempt was made to immobilise the complex MoO2(THF)Cl[(-)-8-phenylthioneomenthol] within the channels of MCM-41 mesoporous silica by using a tethering ligand [L = NC(CH2)(3)Si(OEt)(3)]. The material was characterised by powder X-ray diffraction (XRD), IR spectroscopy and magic-angle-spinning (MAS) NMR (C-13, Si-29). Catalytic examinations demonstrated that it was active in the epoxidation of cyclooctene by TBHP. (C) 2001 Elsevier Science B.V. All rights reserved.
引用
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页码:1 / 10
页数:10
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