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EFFICIENT MOLECULAR CONSTRUCTION BY MULTI-COMPONENT COUPLING REACTIONS IN TRANSITION METAL LIGAND FIELDS

过渡金属配体场中多组分偶联反应的高效分子构建

基本信息

批准号：
09305059
负责人：
ITOH Kenji
金额：
$ 20.29万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09305059/
关键词：
Transition metal complex catalysts Catalytic carbon bond formation Carbocycle synthesis Ruthenium complex catalysts Rhodium complex catalysts Palladium complex catalysts Organotitanium reagents Carbonylation 三成分連結触媒プロセスドミノ付加環化ラジカル環化

项目摘要

1. The aim of this research project is to develop novel transition metal mediated reactions to construct complex molecular structures. The following research results were obtained in active research conducted from 1997 to 2000 fiscal years.2. (1) Highly selective cross-coupling between 1,6-diynes and linear or cyclic alkenes involving heteroatoms or terminal alkynes in the presence of organoruthenium catalysts by way of metallacyclopentadiene intermediates. Unprecedented new domino couplings of dynes with bicyclic alkenes. (2) Based on the mechanistic aspects of rhodium-catalyzed silylformylation of an alkynes, the construction of cyclopentenones, as well as, four-component coupling of an alkynes, a hydrosilane, carbon monoxide, and pyrrolidine was found. (3) Rhodium-carbonyl catalyzed silylative carbocyclization of 1,6-enynes. (4) Rhodium-catalyzed hydrosilylation of 1,6-diynes and its extension to new catalytic annelation to CィイD260ィエD2 fullerene. (5) Rhodium-catalyzed construction of heterocycles from propargyl alcohols and amines. (6) Iridium-catalyzed Michael and aldol reaction of silylenol ethers. (7) Palladium(0)-catalyzed cyclization between electron-deficient alkynes and diynes and its extension to new triyne cyclization. (8) Novel keto-nitrile coupling and pinacol coupling of dials by means of paramagnetic organization reagents. (9) New cyclooctatetraene synthesis starting from a zircona- and titannametalacyclopentadienes.

1.本研究项目的目的是开发新型的过渡金属介导的反应来构建复杂的分子结构。在1997至2000财政年度进行的积极研究中，取得了以下研究成果。(1)1，6-二炔与含杂原子或末端炔的直链或环状烯烃之间的高选择性交叉偶联反应，以金属环戊二烯中间体为催化剂。双环烯烃前所未有的新多米诺骨牌偶联。(2)基于Rh催化的炔硅甲酰化反应的机理，发现了环戊烯酮的结构，以及炔烃、氢硅烷、一氧化碳和吡咯烷的四组分偶联反应。(3)1，6-烯炔的硅烷化碳环化反应。(4)Rh催化的1，6-二炔硅氢加成反应及其延伸到C-ィイD260ィエD2富勒烯的新催化环化反应。(5)铑催化的丙炔醇和胺杂环的构筑。(6)Ir催化的硅酚醚的Michael和Aldol反应。(7)钯(0)催化的缺电子炔烃与二炔的环化反应及其扩展到新的三炔环化反应。(8)利用顺磁性组织试剂实现新型的酮腈偶联和片呐醇偶联。(9)以锆石和钛氨基杂环戊二烯为起始原料合成新的环辛四烯。