Conversion of meso-alkenes to chiral alkenes via titanocene-catalyzed ring-opening/ring-closing olefin metathesis

被引：9

作者：

Halterman, RL ^{[1
]}

Ramsey, TM ^{[1
]}

机构：

[1] Univ Oklahoma, Dept Chem & Biochem, Norman, OK 73019 USA

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1997年 / 547卷 / 01期

基金：

美国国家卫生研究院;

关键词：

olefin metathesis; chiral bis(cyclopentadienyl)titanium dichloride; titanacyclobutanes; stereoselective synthesis; titanium; carbene;

D O I：

10.1016/S0022-328X(97)00203-9

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The preparation of 7-anti-(3-methyl-3-butenyl)norbornene 11 is described. This meso-symmetrical diene underwent ring opening/ring-closing olefin metathesis catalyzed by bis(cyclopentadienyl)titanacyclobutane 4 to give (1R*,6R*,7S*)-7-ethenyl-3-methylbicyclo[4.3.0]non-2-ene as a single diastereomer. The less-substituted 7-anti-(3-butenyl)norbornene 1 did not react selectively at the norbornene double bond. Related 7-ester-substituted norbornenes underwent stoichiometric ring-opening/ring-closing olefin metathesis to give single diastereomers of bicyclic ketones after acidic work-up. Attempts to form a chiral Tebbe-type complex from ansa-(2,2'-bis[8-(bicyclo[4.3.0]-nona-1(6),7-dienyl)]-1, 1'-binaphthyl)titanium dichloride 18 or a reactive chiral titanium carbene intermediate from its dimethyl derivative 20 were unsuccessful. (C) 1997 Elsevier Science S.A.

引用

页码：41 / 48

页数：8

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