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Development of Highly Efficient Catalytic C-C Bond-Forming Reactions Bosed or Conplex Induced Proximity Effect

高效催化 C-C 键形成反应的开发

基本信息

批准号：
13650902
负责人：
ITAMI Kenichiro
金额：
$ 2.3万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

The use of dimethyl(2-pyridyl)silyl group (2-PyMe_2Si group) as a removable catalyst-directing group was found to be a powerful strategy for enhancing the efficiency of otherwise sluggish catalytic carbon-carbon bond-forming reactions by taking advantage of attractive substrate-catalyst interaction.For example, the palladium-catalyzed Mizoroki -Heck-type reaction of 2-pyridyldimethyl(vinyl)silanes with organic iodides took place in the presence of Pd_2(dba)_3/P(2-furyl)_3 catalyst to give β-substituted vinylsilanes in excellent yields. The Heck-type coupling occurred even with α- and β-substituted 2-pyridyldimethyl(vinyl)silanes. The one-pot double Mizoroki-Heck-type reaction of 2-pyridyldimethyl(vinyl)silane took place with two different aryl iodides to afford β,β-diarylated vinylsilanes in good yields.A "hard-to-achieve" catalytic intermolecular Pauson-Khand-type reaction was also facilitated by 2-PyMe_2Si group. In the presence of a catalytic amount of Ru_3(CO)_<12>, intermolecular Pauson -Khand-type reaction of alkyne, alkenyldimethyl(2-pytidyl)silane, and carbon monoxide took place to afford various substituted 2-cyclopentenones in good to high yields. The use of removable directing 2-PyMe_2Si group not only realizes a formal catalytic intermolecular Pauson-Khand-type reaction using unstrained alkenes which was previously difficult to achieve, but also realizes acomplete regioselective incorporation of substituents at 4- and 5-positions of 2-cyclopentenone structure.

使用二甲基（2-吡啶基）甲硅烷基（2-PyMe_2Si基团）作为可去除的催化剂导向基团被发现是通过利用有吸引力的底物-催化剂相互作用来提高否则缓慢的催化碳-碳键形成反应的效率的有力策略。在Pd_2（dba）_3/P催化下，2-吡啶基二甲基（乙烯基）硅烷与有机碘化物发生了Mizoroki-Heck型反应，2-呋喃基）_3催化合成β-取代乙烯基硅烷。Heck型偶联甚至发生在α-和β-取代的2-吡啶基二甲基（乙烯基）硅烷。2-吡啶基二甲基（乙烯基）硅烷与两种不同的碘代芳基发生了一锅双Mizoroki-Heck反应，得到了高产率的β，β-二芳基化乙烯基硅烷; 2-PyMe_2Si基团还促进了“难以实现”的分子间Pauson-Khand反应。在催化量的Ru_3（CO）_3存在下<12>，炔、烯基二甲基（2-吡啶基）硅烷和CO发生分子间Pauson-Khand反应，高产率地得到了各种取代的2-环戊烯酮。可除去的2-PyMe_2Si定向基团的使用不仅实现了以前难以实现的无张力烯烃的形式催化分子间Pauson-Khand型反应，而且实现了2-环戊烯酮结构的4-和5-位取代基的完全区域选择性引入。