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Development of practical catalytic asymmetric processes based on binuclear metal complexes

基于双核金属配合物的实用催化不对称过程的开发

基本信息

批准号：
14370715
负责人：
HASHIMOTO Shunichi
金额：
$ 9.22万
依托单位：
HOKKAIDO 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 2004
项目状态：
已结题

项目摘要

1.We have found that the enantioselective intramolecular C-H insertion reaction of aryldiazoacetates catalyzed by dirhodium tetrakis[N-phthaloyl-(S)-tert-leucinate], Rh_2(S-PTTL)_4, proceeded at -78 ℃ to provide exclusively cis-2-aryl-3-methoxycarbonyl-2,3-dihydobenzofurans in up to 94% ee.We have also found that Rh_2(S-PTTL)_4-catalyzed intramolecular C-H insertion reaction of α-diazoester gave cis-2-arylcyclopentanecarboxylate with up to 97% ee.2.Dirhodium(II) tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate], Rh_2(S-TFPTTL)_4, in which the phthalimido hydrogen atoms of the parent dirhodium(II) complex are substituted by fluorine atoms, dramatically enhances the reactivity and enantioselectivity (up to 97% ee) in intramolecular aromatic C-H insertion reactions of methyl 4-alkyl-2-diazo-4,4-diphenyl-3-oxopropionates. Catalysis with the use of 0.001 mol % of Rh_2(S-TFPTTL)_4 has achieved the highest turnover number (up to 98,000 with the methyl substituent) ever recorded for chiral dirhodium(II) complex-catalyzed carbene transformations, without compromising the yield or enantioselectivity. We also found that Rh_2(S-TFPTTL)_4 has been found to be well suited for enantioselective nitrene transfer reaction of silyl encl ether with [(2-nitrophenyl)sulfonylimino]phenyliodinane. The observed enantioselectivity of up to 99% ee is the highest reported to date for dirhodium(II) complex-catalyzed nitrene transformations.3.We have found that enantioselective 1,3-dipolar cycloaddition of the keto-carbonyl ylide with aromatic aldehyde has been effected with the aid of Rh_2(S-BPTV)_4, affording cycloadducts with perfect exo-selectivity and enantioselectivities in excess of 92%. We also found that cycloaddition of keto-carbonyl ylide derived from α-diazo-β-ketoester with ethynylarenes under the influence of Rh_2(S-TCPTTL)_4 afforded cycloadduct in 97% ee.

1.我们发现四[N-邻苯二甲酰-(S)-叔亮氨酸]二铑Rh_2(S-PTTL)_4在-78 ℃催化芳基重氮乙酸酯的对映选择性分子内C-H插入反应，独家提供顺-2-芳基-3-甲氧基羰基-2,3-二氢苯并呋喃，ee高达94%。我们还发现Rh_2(S-PTTL)_4催化α-重氮酯的分子内C-H插入反应，得到了ee高达97%的顺-2-芳基环戊烷甲酸酯。2.二铑(II) 四[N-四氟邻苯二甲酰-(S)-叔亮氨酸]，Rh_2(S-TFPTTL)_4，其中母体二铑(II)配合物的邻苯二甲酰亚胺氢原子被氟原子取代，显着增强了分子内芳香族C-H插入的反应活性和对映选择性（高达97% ee） 4-烷基-2-重氮-4,4-二苯基-3-氧代丙酸甲酯的反应。使用 0.001 mol % 的 Rh_2(S-TFPTTL)_4 进行催化，实现了手性二铑 (II) 络合物催化卡宾转化记录中最高的转换数（甲基取代基时高达 98,000），且不影响产率或对映选择性。我们还发现Rh_2(S-TFPTTL)_4非常适合硅环醚与[(2-硝基苯基)磺酰亚氨基]苯基碘的对映选择性氮宾转移反应。观察到的对映选择性高达 99% ee，是迄今为止报道的二铑(II)配合物催化氮宾转化的最高值。 3.我们发现，酮基叶立德与芳香醛的对映选择性 1,3-偶极环加成反应在 Rh_2(S-BPTV)_4 的帮助下进行，得到了具有完美的环加成物。外型选择性和对映选择性超过92%。我们还发现，在Rh_2(S-TCPTTL)_4的影响下，α-重氮-β-酮酯衍生的酮-羰基叶立德与乙炔基芳烃发生环加成反应，得到97% ee的环加成物。