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CARBON-CARBON BOND FORMATION BY USE OF ORGANOZIRCONIUM COMPLEX UNDER TRANSITION-METAL CATALYST

过渡金属催化剂下使用有机锆络合物形成碳-碳键

基本信息

批准号：
16590017
负责人：
HANZAWA YUJI
金额：
$ 2.37万
依托单位：
SHOWA PHARMACEUTICAL UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

Organozirconocene chloride complex, which is known to be a poor nucleophile, showed the enhanced nucleophilicity under transition-metal catalyzed conditions. Thus, alkenylzirconocene chloride complex reacted with α,β-unsaturated carbonyl compounds to give 1,4-addition products in the presence of Rh(I) catalyst. The reaction was extended to α,β-unsaturated compounds, which have a chiral amides auxiliary, and we found that the product was obtained in high diastereoselectivity, thus in optically pure state. Acylzirconocene chloride complex, which has been established as an acyl anion donor by us, showed further usefulness for the formation of carbocyclic compounds. Thus, the Pd-catalyzed reactions of acylzirconocene chlorides with co-alkenyl or-alkynyl α,β-enones afforded bicyclo[3.3.0]compounds, stereoselectively. Interestingly, the reaction of α,w-unsaturated compounds, which possess no α,β-enone functionality, was catalyzed by Ni catalyst to give bicylo[3.1.0] compounds.The continuing study on the chemistry of low valent zirconocene complex, which can be generated by treating zirconocene dichloride with n-BuLi, indicated that an efficient formation of benzylic zirconocene complex by treating o-alkoxymethl styrene with low valent zirconocene. Formation of carbon-carbon bond from thus generated zirconocene complex was carried out in the presence of Cu catalyst, and thus the important intermediate for the preparation of estrone was efficiently generated by our zirconocene/metal catalyst chemistry.Elucidations on the nucleophilic reactivity and the synthetic application of organozirconocene complex are our current very active research project, thus we continue the organozirconocene chemistry to find a new and noble carbon-carbon forming reaction.

有机氯化锆络合物是一种较差的亲核剂，在过渡金属催化条件下表现出较强的亲核性。因此，在Rh(I)催化剂存在下，烯基氯化锆络合物与α，β-不饱和羰基化合物反应生成1，4-加成产物。将反应扩展到具有手性酰胺辅助的α，β-不饱和化合物，我们发现产物以高的非对映选择性得到，从而处于光学纯态。我们作为酰基阴离子供体的酰基二茂锆氯络合物在碳环化合物的形成中显示出更大的应用价值。因此，钯催化的二茂锆氯化物与共烯基或-炔基α，β-烯酮的反应，立体选择性地得到了双环[3.3.0]化合物。有趣的是，不具有α-烯酮官能团的α，β，w-不饱和化合物在镍催化剂的催化下反应生成了双基[3.1.0]化合物。对二氯化锆与n-BuLi反应生成低价的二茂锆络合物的持续研究表明，邻烷氧基甲基苯乙烯与低价二茂锆制得的低价二茂锆络合物是一种有效的合成方法。在铜催化剂的存在下，由生成的茂锆络合物形成碳-碳键，从而有效地生成了制备雌酮的重要中间体。亲核反应活性的评价和有机茂锆络合物的合成应用是我们目前非常活跃的研究项目，因此，我们继续进行有机茂锆化学，寻找一种新的高贵的碳-碳构型反应。