Development of New Catalytic Reactions Based on Novel Approach for Carbene Complexes

基于卡宾配合物新方法开发新催化反应

基本信息

批准号：
14350468
负责人：
OHE Kouichi
金额：
$ 9.73万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

General principles for generating alkylidene-and vinylidene-complexes from alkynes were found to apply ~to transition metal-catalyzed reactions. Intramolecular cyclization or migration in pre-formed π-alkyne complexes occurs to give an alkylidene-or a vinylidene-complex.We have demonstrated that 2-pyranylidene-chromium complexes were prepared from (β-ethynyl-α,β-unsaturated esters and amides in the presence of triethylamine. A chromium-vinylidene complex is a key intermediate in the reaction. Application of this protocol to cis-l-ethynyl-2-acylcyclopropane provided a new catalytic aromatization reaction leading to o-substituted phenol via cyclopropylvinylidenes. In sharp contrast, the reaction of β-ethynyl-α,β-unsaturated ketones with M(CO)_5(THF) (M=Cr, W) gave, (2-furyl)carbene complexes selectively via nucleophilic attack of a carbonyl oxygen to a π-alkyne complex. This (2-furyl)carbene complex formation has been nicely applied to catalytic reactions using β-ethynyl-α,β-unsaturated … More ketones, in which cyclopropanation of alkenes, carbene transfer reactions with heteroatoms, and insertion reactions with hydrocarbons have, been demonstrated. Heteroaromatic ring-substituted carbene species, i.e. (2-pyrrolyl)carbenoids were also prepared from the corresponding β-ethynyl-α,β-unsaturated imino compounds.Application to propargylic carboxylates has provided new access to vinylcarbenoids of transition metals. Thus, the nucleophilic attack of a carbonyl oxygen to an internal carbon in π-complexes of propargylic substrates followed by bond cleavage at propargylic position gave vinylcarbene complexes. A wide range of transition metal complexes is effective for the purpose. Particularly, a [RuCl_2(CO)_3]_2 complex as a catalyst can promote the intermolecular cyclopropanation of alkenes using propargylic carboxylates as precursors of vinylcarbenoids. The reaction of conjugated dienes with propargylic substrates afforded seven-membered rings via cyclopropanation and subsequent [3,3]sigmatropic rearrangement. Less

发现从炔烃中产生烷基丙烯和乙烯基 - 复合物的一般原则可用于过渡金属催化的反应。在预成型的π-阿尔基因复合物中，发生分子内环化或迁移，给出了烷基二烯 - 乙烯基二烯 - 复合物。我们证明，由β-乙基-α，β-乙基 - β-饱和酯和酰胺中的triethylimine nementy in kemeneyl in tri-ethylim nyyl sy Is基因组成的β-乙基 - α-乙基-α制备了2-丙二醇 - 氯铵络合物。该方案在顺式-L-乙基-2-酰基环丙烷中的应用提供了新的催化芳香化反应，导致O型环丙基苯基苯酚在急剧的对比度中，β-乙基 - β-元素与M（CO）_5（co）_5（MM = MM = MM = cr）使用β-乙基α，β-β-甲基，β-乙烯的反应很好地应用于π-烷基复合物还从相应的β-乙基-α，β-不饱和免疫化合物中制备了碳烯种类，即（2-吡咯酯）类carbenoids。对丙泊羧酸盐的应用为过渡金属的乙烯基碳苯甲酸酯提供了新的访问。这就是羰基氧对propgylic底物的π复合物中内部碳的核植物攻击，然后在propgylical位置进行键裂解，从而产生了乙烯基碳酸盐络合物。广泛的过渡金属配合物对目的有效。特别是，作为催化剂作为催化剂的[Rucl_2（CO）_3] _2复合物可以使用丙烯酸羧酸盐作为乙烯基癌的前体促进烷烃的分子间环植物。共轭二烯与propgylic底物的反应通过环丙烷和随后的[3,3] Sigmatropic重排提供了七元的环。较少的