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Efficient Organic Reactions by Dynamic Control of Early Transition Metal Complexes

通过动态控制早期过渡金属配合物实现高效有机反应

基本信息

批准号：
14078219
负责人：
TAKAI Kazuhiko
金额：
$ 18.18万
依托单位：
Okayama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

1. Selective Transformations with Novel Organochromium Species : The family of trans-iodocyclo-propanes are good precursors for constructing cyclopropyl-cyclopropyl and-vinyl carbon skeletons. We have found that iodocyclopropanation of terminal alkenes proceeds with organochromium species generated by chromium(II)-reduction of iodoform in the presence of TEEDA (N,N,N',N'-tetraethylethylenediamine) under high stereocontrol. The transformation proceeds smoothly without the presence of a hydroxy or an alkoxy group near the double bond, which is necessary for the cyclopropanation of iodoalkenes with zinc carbenoids.2. Synthesis and Reactions of Tantalum η^2-Bis(trimethylsilyl)acetylene Complex : A tantalum-alkyne complex TaCl_3(Me_3SiC≡CSiMe_3)(dme) (1, DME=1,2-dimethoxyethane) is synthesized by treatment of the corresponding alkyne with a low-valent tantalum derived by reduction of TaCl_5 with zinc in a mixed solvent of toluene and DME according to our previously reported procedure. The t … More antalum complex 1 reacts with an internal alkyne to give a corresponding alkyne complex via ligand exchange reaction. The mechanism of the ligand exchange is clarified by kinetic study of the formation of diphenylacetylene complex from 1 and diphenylacetylene.3. Carbon-Hydrogen Bond Activation with Rhenium Catalysts and Its Application to Organic Synthesis : A rhenium complex, [ReBr(CO)_3(thf)]_2, catalyzes the reaction of an aromatic aldimine with an isocyanate and an acetylene to give a phthalimidine and an indene derivative in a quantitative yield, respectively. The reactions proceed via C-H bond activation, insertion of the isocyanate or the acetylene, intramolecular nucleophilic cyclization to the aldimine of the generated amido-or alkenyl-rhenium species, and reductive elimination. In contrast to ruthenium and rhodium catalysts, which are usually employed in this type of reaction, the rhenium catalyst promotes the insertion of a polar unsaturated molecule. The rhenium-catalyzed reaction of an aromatic ketimine with ethyl acrylate gave an indene derivative in good yield via C-H bond activation. The indene derivatives could also be obtained by the reactions of aromatic ketones with α,β-unsaturated esters in the presence of catalytic amounts of the rhenium complex andp-anisidine. Less

1.新型有机铬物种的选择性转化：反式碘代环丙烷家族是构建环丙基-环丙基和-乙烯基碳骨架的良好前体。我们已经发现，在高度立体控制下，在TEEDA（N，N，N ′，N ′-四乙基乙二胺）存在下，通过碘仿的铬（II）还原产生的有机铬物质进行末端烯烃的碘环丙烷化。该转化过程顺利进行，而不存在双键附近的羟基或烷氧基，这是碘代烯烃与类卡宾锌的环丙烷化所必需的。钽η^2-双（三甲基硅基）乙炔配合物的合成与反应：在甲苯和DME的混合溶剂中，用TaCl_5与锌还原得到低价钽，再与相应的炔反应，合成了钽-炔配合物TaCl_3（Me_3SiC <$CSiMe_3）（dme）（1，DME= 1，2-二甲氧基乙烷）。的t ...更多信息镧配合物1与内炔反应，通过配体交换反应得到相应的炔配合物。通过对1与二苯乙炔形成二苯乙炔配合物的动力学研究，阐明了配体交换的机理.铼催化剂活化碳-氢键及其在有机合成中的应用：铼配合物[ReBr（CO）_3（thf）]_2催化芳香醛亚胺与异氰酸酯和乙炔的反应，分别以定量产率生成苯并吡咯酮和茚衍生物。该反应通过C-H键活化、异氰酸酯或乙炔的插入、分子内亲核环化为所产生的酰胺基或烯基-氨基物种的醛亚胺以及还原消除来进行。与通常用于这种类型的反应的钌和铑催化剂相反，该催化剂促进极性不饱和分子的插入。在铑催化下，芳香酮亚胺与丙烯酸乙酯反应，通过C-H键活化，以较高的产率得到茚衍生物。芳酮与α，β-不饱和酯在催化量的对甲氧基苯胺和络合物存在下反应也可得到茚衍生物。少