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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.研究发现，四氢呋喃[N-邻苯二甲酰基-(S)-叔亮氨酸]，Rh_2(S-PtTl)_4，我们还发现，Rh_2(S-cis-2-aryl-3-methoxycarbonyl-2，3-dihydobenzofurans)_4催化的重氮酯的分子内C-H插入反应得到了顺式-2-芳基环戊烷羧酸盐，EE值高达97%。2.Dirhodium(II)tetrakis[N-tetrafluorophthaloyl-(S)-tert-leucinate]，Rh_2(S-℃)_4，其中母体α(II)的邻苯二甲酰亚胺氢原子被氟原子取代，显著提高甲基4-alkyl-2-diazo-4，4-diphenyl-3-oxopropionates.分子内芳香族C-H插入反应的活性和对映体选择性(最高可达97%ee)当Rh_2(S-TFPTTL)_4的摩尔分数为0.001%时，在不影响产率和对映体选择性的前提下，获得了最高的转化率(甲基取代基最高达98,000)。我们还发现，Rh_2(S-TFPTTL)_4非常适合于硅醚与[(2-硝基苯基)磺酰亚氨基]苯基碘烷的不对称转移反应。3.我们发现在Rh_2(S-bptv)_4的作用下，酮-羰基叶立德与芳香醛的1，3-偶极环加成反应是进行的，得到的环加成产物具有良好的外选择性和92%以上的对映体选择性。我们还发现α-重氮-β-酮酯在Rh_2(S-TCPTTL)_4的作用下与乙炔基芳烃的环加成反应在97%ee中得到环加成产物。