Development of Catalytic Enantioselective Reactions Based on the Activation Technology by Chiral Ligands
基于手性配体活化技术的催化对映选择性反应研究进展
基本信息
- 批准号:10470468
- 负责人:
- 金额:$ 8.19万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (B)
- 财政年份:1998
- 资助国家:日本
- 起止时间:1998 至 2001
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
We have developed three types of new activation technology ; the activation of lithium ester enolates by a chiral lithium amide having ether moiety (1), of less reactive organometallic reagents, such as organozinc and organoboran by a complex of a chiral amidophosphine and a transition metal (2), and of lithium thiolate by a chiral amino ether (3).1. In the presence of a chiral lithium amide having ether moiety, thereaction of lithium ester enolates with imines gave β-lactains in up to 96% yield and 74% ee. This technology was also applicable to the addition of lithium ester enolates to α,β-unsaturated esters to give the adducts in up to 67% yield and 92% ee.2. In the presence of a catalytic amount of a chiral amidophosphine and copper(II) triflate ; the reaction of 4,4-dimethyl-2-cyclohexenone and diethylzinc gave the ethyl adduct with 64% ee. The application of this amidophosphine-copper-diethylzinc system to the reaction with imine was successful, giving ethyl adducts in up to 97% y … More ield and 94% ee. Furthermore, the chiral amidophosphine ligand was applicable to the rhodium-arylboronic acid system. In the presence of a catalytic amount of the chiral amidophosphine and rhodium(I), aryl boronic acidsreacted with 2-alkenones to provide 3-arylalkanones in up to 99% yield and 96% ee. We are accumulating the experimental evidence that the chiral amidophosphine ligand is a so-called hemilabile ligand in this rhodium complex.3. In the presence of a chiral amino ether, lithium thiolates added to α,β-unsaturated esters and the resulting lithium ester enolate was enantioselectively protonated. Thus, using α,β-unsaturated esters having no β-substitoent, the addncts with up to 92% ee were obtained. When a chiral α,β-unsaturated ester having formyl group was used as an acceptor, the intermediate lithium enolate reacted withthe formyl group in the intramolecular fashion to give cyclized products in good diastereoselectivity. This cyclization was nicely applied to the synthesis of (-)-neplanocin A. Less
我们已经开发了三种类型的新的活化技术;通过具有醚部分的手性氨基锂(1)来活化锂酯烯醇化物,通过手性氨基膦和过渡金属的络合物(2)来活化反应性较低的有机金属试剂,例如有机锌和有机硼烷,以及通过手性氨基醚(3)来活化锂硫醇。在含醚基的手性氨基锂存在下,烯醇化锂酯与亚胺的加成反应得到β-内酰胺,产率高达96%,ee值为74%,该技术也适用于烯醇化锂酯与α,β-不饱和酯的加成反应,产率高达67%,ee值为92%.在催化量的手性氨基膦和三氟甲磺酸铜(Ⅱ)存在下,4,4-二甲基-2-环己烯酮与二乙基锌反应,得到64%ee的乙基加合物.将此氨基膦-铜-二乙基锌体系应用于与亚胺的反应,得到97%ee的乙基加合物 ...更多信息 此外,该手性氨基膦配体适用于铑-芳基硼酸体系。在催化量的手性氨基膦和铑(I)存在下,芳基硼酸与2-烯酮反应生成3-芳基烷酮,产率高达99%,ee值为96%.在手性氨基醚存在下,硫醇锂与α,β-不饱和酯加成,生成的烯醇化酯锂对映选择性质子化。因此,用不含β-取代基的α,β-不饱和酯,可得到ee值高达92%的加成物。以带甲酰基的手性α,β-不饱和酯为受体,烯醇化锂与甲酰基以分子内方式反应,得到具有良好非对映选择性的环化产物。该环化反应很好地应用于(-)-neplanocin A的合成。少
项目成果
期刊论文数量(82)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
K.Tomioka: "Efficient Cyclization of ω-Oxo-α,β-Unsaturated Esters Using Lithium Thiolate-Initiated Michael-Aldol Tandem Reaction"Tetrahedron Lett.. 40・38. 6979-6982 (1999)
K. Tomioka:“利用硫醇锂引发的 Michael-Aldol 串联反应有效环化 ω-Oxo-α,β-不饱和酯” Tetrahedron Lett.. 40・38 (1999)。
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- 影响因子:0
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K.Tomioka: "A Facile and Efficient Asymmetric Synthesis of (+)-Salsolidine"Tetrahedron Lett.. 41・29. 5533-5536 (2000)
K. Tomioka:“(+)-Salsolidine 的简便高效的不对称合成” Tetrahedron Lett.. 41・29 (2000)
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- 影响因子:0
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K.Tomioka: "Enantioselective Conjugate Addition of Organometallic Reagents to Cycloalkenones by the Aid of Chiral Lactam-Phosphine Ligand"Heterocycles. 52. 95-97 (2000)
K.Tomioka:“借助手性内酰胺-膦配体将有机金属试剂对环烯酮进行对映选择性共轭加成”杂环。
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- 发表时间:
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- 影响因子:0
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M.Ono: "Total Synthesis of (-)-Neplanocin A by Using Lithium Thiolate-Initiated Michael-Aldol Tandem cyclization Reaction"J. Org. Chem.. 66. 8199-8203 (2001)
M.Ono:“利用硫醇锂引发的Michael-Aldol串联环化反应全合成(-)-Neplanocin A”J。
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- 影响因子:0
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K.Tomioka: "Chiral Ketone-Catalyzed Asymmetric Epoxidation of Stilbene with Oxone"Heterocycles. 54・2. 615-617 (2001)
K. Tomioka:“手性酮催化二苯乙烯与 Oxone 的不对称环氧化”杂环 54・2 (2001)。
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TOMIOKA Kiyoshi其他文献
TOMIOKA Kiyoshi的其他文献
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{{ truncateString('TOMIOKA Kiyoshi', 18)}}的其他基金
Asymmetric Addition of carbon, nitrogen, oxygen and sulfur nucleophiles and its application to the synthesis of biologically active compounds
碳、氮、氧、硫亲核试剂的不对称加成及其在生物活性化合物合成中的应用
- 批准号:
20249002 - 财政年份:2008
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for Scientific Research (A)
Development of Efficient Cascade Reactions with Unsaturated Carbonyl
不饱和羰基高效级联反应的发展
- 批准号:
17065014 - 财政年份:2005
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Development of asymmetric reactions using multi-reagent complexes
使用多试剂复合物开发不对称反应
- 批准号:
15390005 - 财政年份:2003
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Origin of Regio and Stereoselectivity in Conjugate Addition Reactions
共轭加成反应中区域和立体选择性的起源
- 批准号:
07457520 - 财政年份:1995
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Catalytic Asymmetric Synthesis of Bioactive Molecules
生物活性分子的催化不对称合成
- 批准号:
07557139 - 财政年份:1995
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for Scientific Research (A)
Catalytic Asymmetric Synthesis of Functional Chiral Molucules
功能手性分子的催化不对称合成
- 批准号:
05453181 - 财政年份:1993
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for General Scientific Research (B)
Asymmetric Synthesis Using Chiral Lewis Base
使用手性路易斯碱的不对称合成
- 批准号:
04557097 - 财政年份:1992
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for Developmental Scientific Research (B)
A Short Asymmetric Synthesis of Podophyllotoxin Related Antitumor Agent
鬼臼毒素相关抗肿瘤药物的简短不对称合成
- 批准号:
01571143 - 财政年份:1989
- 资助金额:
$ 8.19万 - 项目类别:
Grant-in-Aid for General Scientific Research (C)
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研究用于开发 3d 过渡金属催化剂的 N-手性配体
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Development of heterogeneous catalyst systems based on bifunctional chiral ligands and finely designed metal nanoparticles
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