DEVELOPMENT OF CATALYTIC ASYMMETRIC REACTIONS USING LANTANOIDS
使用 Lantanoids 催化不对称反应的发展
基本信息
- 批准号:13672207
- 负责人:
- 金额:$ 1.73万
- 依托单位:
- 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
- 来源:
- 关键词:
项目摘要
1) Asymmetric Diels-Alder reactions of cyclopentadiene and several dienophiles catalyzed by a chiral ytterbium complex prepared by a noble axially asymmetric chiral ligand, BINAMIDE and Yb(OTf)_3 were investigated.The reaction with bromoacryloyl amide afforded cyclo-adduct in 97% yield with 98% de and with 93% ee. The adduct was converted cyclosarkomycin, a key intermediate for the synthesis of antitumor antibiotics sarkomycin (overall 6%, 10 steps). Although a diastereoselective synthesis of optically active cyclosarkomycin has been reported, this is the first catalytic enentioselective synthesis cyclosarkomycin.The reaction with a fumaric acid derivative gave a mixture of adduct in 83% yield with 52% de and with 84% ee. The adduct was converted to a key intermediate for the synthesis of TXA2 antagonist, ONO-8809 which was developed by Ono company. This fumaric acid derivative also reacted with siloxydiene to give a cyclohexene derivative with low enantioselectivity (13% ee).2) A new allylic halogenation and Pictet-Spengler reaction of imines, both catalyzed by Yb(OTf)_3 were developed. Asymmetric version of these reactions will be developed in future.
1) 研究了由高贵的轴不对称手性配体 BINAMIDE 和 Yb(OTf)_3 制备的手性镱络合物催化的环戊二烯和几种亲二烯体的不对称 Diels-Alder 反应。与溴代丙烯酰酰胺的反应得到环加合物,收率 97%,de 98%,de 93% ee。加合物转化为环沙霉素,是合成抗肿瘤抗生素沙沙霉素的关键中间体(总产率6%,10步)。尽管已经报道了光学活性环肉霉素的非对映选择性合成,但这是环肉霉素的首次催化对映选择性合成。与富马酸衍生物的反应得到了加合物混合物,收率83%,de 52%,ee 84%。该加合物转化为合成TXA2拮抗剂ONO-8809的关键中间体,由小野公司开发。该富马酸衍生物还与硅氧基二烯反应生成低对映选择性的环己烯衍生物(13% ee)。2)开发了一种新的烯丙基卤化反应和亚胺的Pictet-Spengler反应,均由Yb(OTf)_3催化。这些反应的不对称版本将在未来开发。
项目成果
期刊论文数量(17)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Riichiro Tsuji, Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Pictet-Spengler Reaction of Nitrones and Imines Catalyzed by Yb(OTf)_3-TMSCI"Chem. Lett. 428-429 (2002)
Riichiro Tsuji、Masamichi Yamanaka、Atsushi Nishida、Masako Nakakawa:“Yb(OTf)_3-TMSCI 催化的硝酮和亚胺的 Pictet-Spengler 反应”Chem。
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- 影响因子:0
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Masamichi Yamanaka, Atsushi Nishida, Masako Nakagawa: "Imino Ene Reaction Catalyzed by Ytterbium(III) Triflate and TMSCl or TMSOTf"J. Org.Chem.. 68. 3112-3120 (2003)
Masamichi Yamanaka、Atsushi Nishida、Masako Nakakawa:“三氟甲磺酸镱 (III) 和 TMSCl 或 TMSOTf 催化的亚氨基烯反应”J。
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- 影响因子:0
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Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel Synthetic Method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by Intramolecular Haloamination"Synlett. 1514-1516 (2002)
Mitsuhiro Arisawa、Yuko Ando、Masamichi Yamanaka、Masako Nakakawa、Atsushi Nishida:“通过分子内卤化从 N-乙酰基-2-异丙烯基苯胺合成 2,3-二氢-3-卤代-3-甲基吲哚的新方法”Synlett。
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- 影响因子:0
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Mitsuhiro Arisawa, Yuko Ando, Masamichi Yamanaka, Masako Nakagawa, Atsushi Nishida: "Novel Synthetic Method for 2,3-Dihydro-3-halo-3-methylindole from N-Acetyl-2-isopropenylaniline by Intramolecular Haloamination"Synlett. No.9. 1514-1516 (2002)
Mitsuhiro Arisawa、Yuko Ando、Masamichi Yamanaka、Masako Nakakawa、Atsushi Nishida:“通过分子内卤化从 N-乙酰基-2-异丙烯基苯胺合成 2,3-二氢-3-卤代-3-甲基吲哚的新方法”Synlett。
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- 影响因子:0
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Riichiro Tsuji, Masako Nakagawa, Atsushi Nishida: "Efficient Synthetic Approach to Optically Active β-Carboline Derivatives via Pictet-Spengler Reaction Promoted by Trimethylchlorosilane"Tetrahedron Asymmetry. 14. 177-180 (2003)
Riichiro Tsuji、Masako Nakakawa、Atsushi Nishida:“通过三甲基氯硅烷促进的 Pictet-Spengler 反应实现光学活性 β-咔啉衍生物的高效合成方法”四面体不对称性。
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NISHIDA Atsushi其他文献
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{{ truncateString('NISHIDA Atsushi', 18)}}的其他基金
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饮用水中的锂含量与青少年的心理健康
- 批准号:
22791158 - 财政年份:2010
- 资助金额:
$ 1.73万 - 项目类别:
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21390002 - 财政年份:2009
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A prospective follow up study of adolescents with psychotic like experiences
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- 批准号:
20890293 - 财政年份:2008
- 资助金额:
$ 1.73万 - 项目类别:
Grant-in-Aid for Young Scientists (Start-up)
Synthesis of Biologically Active Alkaloids and Lead Compounds for Drug Development
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16390003 - 财政年份:2004
- 资助金额:
$ 1.73万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Synthesis of New Axially Chiral Ligand Library and Application to Asymmetric Synthesis of Biologically Active Compounds.
新型轴向手性配体库的合成及其在生物活性化合物不对称合成中的应用。
- 批准号:
11672098 - 财政年份:1999
- 资助金额:
$ 1.73万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
DEVELOPMENT OF ASYMMETRIC RADICAL REACTIONS AND APPLICATION TO THE SYNTHESIS OF BIO-ACTIVE COMPOUNDS
不对称自由基反应的发展及其在生物活性化合物合成中的应用
- 批准号:
08672441 - 财政年份:1996
- 资助金额:
$ 1.73万 - 项目类别:
Grant-in-Aid for Scientific Research (C)