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.

有氧化新近氯化物络合物（已知核恐惧症）显示出在过渡金属催化条件下的核恐惧症增强。这就是烷烯基锌氯化氯化物复合物在RH（i）催化剂存在下与α，β-不饱和羰基化合物反应，从而产生1,4-添加产物。该反应扩展到具有手性酰胺辅助的α，β-不饱和化合物，我们发现该产物以高钻石选择性获得，因此在光学上纯净的状态。我们已确定为酰基阴离子供体的酰基二一个新近氯化物络合物对碳化合物的形成显示出进一步的有用性。这是酰基二循环氯与共烷基或碱基αnylα，β-烯酮的PD催化反应，可提供双环[3.3.0]化合物，立体选择。有趣的是，α，W-非饱和化合物的反应是低谷锆二世络合物化学的持续研究，可以通过用N-Buli处理锆二革二氯化，这表明，通过处理O-alalkoxememethl polterencene fital Valent Zirconocene的苯并二世二世复合物的有效形成。 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 effectively generated by our zirconocene/metal catalyst chemistry.Elucidations on the nuclear 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