New synthesis of a seven member ring fused heterocycles using ring expansion reaction of an aromatic ring

利用芳环扩环反应新合成七元环稠合杂环

基本信息

批准号：
19590009
负责人：
AOYAMA Toyohiko
金额：
$ 2.83万
依托单位：
Nagoya City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2007
资助国家：
日本
起止时间：
2007 至 2009
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-19590009/
关键词：
ヘテロ環化学トリメチルシリルジアゾメタンアルキリデンカルベンアリールアセチレンアリールプロピオレートピロリジン β-アミノケトンアリール(オキソ)アセテートインダゾール [3+2]環化付加反応 t-ブチル(2-メトキシフェニィル)(オキソ)アセテートベンゾフラン-3-カルボキシレート Buchner反応 2-アザアズレン 2-ジアゾ-2-トリメチルシリルエタノールピラゾール

项目摘要

(1) Ketones reacted with magnesium bromide salt of trimethylsilyldiazomethane (TMSCHN_2) to give the corresponding 2-diazo-2-(trimethylsilyl)ethanols which were easily converted to pyraazoles by 1,3-dipole cycloaddition the reaction with acetylenes. (2) Aryl and heteroaryl aldehydes were easily converted to functionalized acetykenes in on-pot using lithium salt of TMSCHN_2. (3) TMSCHN_2 reacted with thiobenzoyl isocyanates to give the corresponding diazoketones which were converted to 2-azaazulenes by treatment with rhodium acetates. (4) Diazo(trimethylsilyl)methylmagnesium bromide smoothly reacted with t-butyl aryl(oxo)acetates to afford the corresponding arylpropiolates via alkylidenecarbene intermediates. (5) Diazo(trimethylsilyl)methylmagnesium bromide readily reacted with ketones and aldehydes to give 2-diazo-(2-trimethylsilyl)ethanoles which were efficiently converted to indazoles bearing a hydroxmethyl unit at 3-position by intermolecular [3+2]cycloaddition with benzynes. (6) Diazo(trimethylsilyl)methylmagnesium bromide reacted with (o-methoxyphenyl)(oxo)acetates to readily afford 2-unsubstituted benzofuran-3-carboxylates via oxonium ylides formed from the initially generated alkylidenecarbene intermediates. (7) Lithium trimethylsilyldiazomethane reacted with N-benzyl-β-aminoketones at -78℃in THF to give 3-substituted 1-benzyl-3-(trimethylsiloxy)pyrrolidines in moderate to good yields.

（1）具有三甲基二甲甲烷的溴化镁盐（TMSCHN_2），使Corresspond的乙醇很容易通过1,3-二极环节转化为吡az醇，该反应与乙酰苯基和杂型甲基化的作用。在使用TMSCHN_2的锂盐中，enzoyl异氰酸酯提供相应的重叠酮，通过对乙酸若菌的信任转化为2-余生。通过ylidenecarbene中间体（2-三甲基甲硅烷基）通过ylidenecarbene中间体进行芳基丙烯酸酯。）ACETT可以通过oxonium通过Oxonium产生的2-无缩合的苯并呋喃-3-羧酸盐，最初产生的烷基肾上腺素。三甲基氧基）吡咯质性中等至良好的产率。