期刊
INORGANICA CHIMICA ACTA
卷 402, 期 -, 页码 140-155出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2013.04.008
关键词
Chiral Schiff-base ligand; Titanium complex; Synthesis; Crystal structure; Asymmetric hydrophosphonylation
资金
- National Natural Science Foundation of China [21074013, 21172022, 21272026]
- Program for New Century Excellent Talents in University [NCET-10-0253]
- Fundamental Research Funds for the Central Universities
- Beijing Municipal Commission of Education
A series of chiral organo-titanium complexes have been prepared from the reaction between Ti((OPr)-Pr-i)(4) and chiral biaryl Schiff-base ligands 1H(2)-12H. The steric demand of the ligand plays an important role in the formation of the titanium complexes. For example, treatment of ligand 1H(2) with 1 equiv of Ti((OPr)-Pr-i)(4) in toluene at room temperature gives, after recrystallization from a toluene solution, the chiral bis-ligated titanium complex (L1)(2)Ti (14). While under similar reaction conditions, the more bulky ligands 2H(2), 4H(2), and 6H(2) form the mono-ligated titanium complexes (L2)Ti((OPr)-Pr-i)(2) (15), (L4)Ti((OPr)-Pr-i)(2)(19), and (L6)Ti((OPr)-Pr-i)(2) (22), respectively, in good yields. The mono-ligated titanium alkoxides can be converted to bis-ligated complex via ligand redistribution reaction. For one instance, treatment of mono-ligated complex (L2)Ti((OPr)-Pr-i)(2) (15) in benzene at 60 degrees C results in the isolation of the bis-ligated complex (L2)(2)Ti (16) in 92% yield. All titanium complexes have been characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of complexes 14-21, 23, 24 and 29 have further been confirmed by X-ray diffraction analyses. The titanium complexes are active catalysts for the asymmetric hydrophosphonylation of aromatic aldehydes with moderate enantioselectivities. (C) 2013 Elsevier B.V. All rights reserved.
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