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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16590017/
• 关键词: alkenylzirconocene; acylzirconocene; low valent zirconocene complex; transition-metal catalyst; nucleophilic reaction; bicycle cyclization; diastereoselectivity; chiral auxiliary; ニッケル; パラジウム; 触媒; ジルコノセン-ブテン錯体; ロジウム; ジルコノセン等価体

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.

有机锆茂氯化物配合物是一种不良亲核试剂，在过渡金属催化条件下表现出增强的亲核性，因此，烯基锆茂氯化物配合物与α,β-不饱和羰基化合物在存在下反应生成1,4-加成产物。 Rh(I)催化剂将反应扩展到具有手性酰胺助剂的α,β-不饱和化合物。发现产物以高非对映选择性获得，因此处于光学纯状态，我们将其作为酰基阴离子供体，显示出对于碳环化合物的形成的进一步有用性。酰基二茂锆与共烯基或炔基α,β-烯酮形成双环[3.3.0]化合物，立体选择性匿名，不具有α，β-烯酮官能团的α，W-不饱和化合物在Ni催化剂的催化下反应生成双环[3.1.0]化合物。低价二茂锆配合物化学的持续研究，可以通过用正丁基锂处理二氯化锆来生成，表明通过处理邻烷氧基甲基可以有效地形成苄基锆茂络合物苯乙烯与低价锆茂在Cu催化剂存在下形成碳-碳键，从而通过我们的锆茂/金属催化剂化学有效地生成了制备雌酮的重要中间体。有机锆茂络合物的亲核反应性和合成应用是我们当前非常活跃的研究项目，因此我们继续有机锆茂化学寻找新颖而高贵的碳-碳形成反应。

项目成果

Copper-catalyzed allylations of Zirconocene intermediate generated from o-alkenyl or o-alkynylbenzyl ether derivatives and zirconocene-butene complex

由邻烯基或邻炔基苄基醚衍生物和茂锆-丁烯络合物生成的茂锆中间体的铜催化烯丙基化

• 发表时间: 2005
• 期刊: J. Org. Chem. 70
• 作者: Ikeuchi;Y;Taguchi;Hanzawa;Y.
• 通讯作者: Y.

Zirconocene-mediated and/or catalyzed unprecedented coupling reactions of al koxymethyl-substituted styrene derivatives

二茂锆介导和/或催化的烷氧基甲基取代苯乙烯衍生物的前所未有的偶联反应

• 发表时间: 2005
• 期刊: J. Org. Chem. 70
• 作者: Ikeuchi;Y.
• 通讯作者: Y.

Copper-catalyzed allylations of zirconocene intermediates generated from o-alkenyl or o-alkynylbenzyl ether derivatives and zirconocene butane complex

由邻烯基或邻炔基苄基醚衍生物和茂锆丁烷配合物生成的茂锆中间体的铜催化烯丙基化

• 发表时间: 2005
• 期刊: J.Org.Chem. 70
• 作者: Hanzawa;Y.et al.
• 通讯作者: Y.et al.

Copper-catalyzed allylations of Zirconocene intermediate generated from o-al kenyl or o-alkynylbenzyl ether derivatives and zirconocene-butene complex

由邻烯基或邻炔基苄基醚衍生物和茂锆-丁烯络合物生成的茂锆中间体的铜催化烯丙基化

• 发表时间: 2005
• 期刊: J. Org. Chem. 70
• 作者: Ikeuchi;Y.
• 通讯作者: Y.

Cyclization/acylation reactions by nickel-catalyzed reactions of 1,6-ynal and 1,6-enyne derivatives with acylzirconocene chloride

• DOI: 10.1016/j.tetlet.2006.01.101
• 发表时间: 2006-03
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: A. Saito;Yusuke Oka;Yohei Nozawa;Y. Hanzawa