Development of Asymmetric Reactions by use of Chiral Bronsted Acid
使用手性布朗斯台德酸开发不对称反应
基本信息
- 批准号:15550042
- 负责人:
- 金额:$ 2.5万
- 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:2003
- 资助国家:日本
- 起止时间:2003 至 2004
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
Development of novel efficient catalysts continue to be a challenging topics in synthetic organic chemistry. We have synthesized a cyclic phosphoric acid derivatives, starting from (R)-BINOL. The phosphoric acid exhibited excellent catalytic activity in the nucleophilic addition reaction toward imines.1) Mannich-type reaction of silyl enolate to imines.Chiral Bronsted acid catalyzed Mannich-type reaction proceeded smoothly in the presence of 10 mol% of a cyclic phosphate derived from 3,3'-bis(4-nitrophenyl)-substituted binaphthol. β-Amino esters were obtained in high to excellent yields and with excellent enantioselectivities. The substituents on binaphthol played a crucial role in enantioselectivity and reactivity. Imines derived from o-HOC_6H_4NH_2 gave the highest enantioselectivity. Presence of o-hydroxy group is essential for the chiral induction. Based on the results, we would like to propose 9-membered transition state, wherein phosphoryloxygen forms hydrogen bond with OH moiety.2) Hydrophosphonylation reactionHydrophosphonylation of diisopropyl phosphite to imine also took place highly enantioselectively to give α-amino phosphonate in high yields with good to high enantioselectivities. In this case, use of a chiral phosphate bearing 3,5-(CF_3)_2C_6H_3 group on 3,3'-position of binaphthyl ring is essential for attaining high enantio selectivity.3) Cycloaddition reactionAza Diels-Alder reaction of Danishefsky's diene with imine also proceeded smoothly by means of the chiral Bronsted acid catalyst. In this case, 2,4,6-triisopropylphenyl group substituted one gave the best results.Contrary to conventional metal-based chiral catalysts, present Bronsted acid is free from metal and is stable in air. Present catalysts adds a new entry into chiral organocatalysts.
新型高效催化剂的开发仍然是有机合成化学中具有挑战性的课题。我们以(R)-BINOL为原料合成了环状磷酸衍生物。该磷酸在亚胺的亲核加成反应中表现出优异的催化活性。1)硅烯醇化物与亚胺的曼尼希型反应。手性布朗斯台德酸催化的曼尼希型反应在10 mol%的3,3'-双(4-硝基苯基)取代联萘酚衍生的环状磷酸盐存在下顺利进行。 β-氨基酯的产率非常高,并且具有优异的对映选择性。联萘酚上的取代基在对映选择性和反应性中起着至关重要的作用。由o-HOC_6H_4NH_2 衍生的亚胺具有最高的对映选择性。邻羟基的存在对于手性诱导是必需的。基于这些结果,我们提出了9元过渡态,其中磷酰氧与OH部分形成氢键。2)氢膦酰化反应亚磷酸二异丙酯与亚胺的氢膦酰化也发生了高度对映选择性,以高产率得到α-氨基膦酸酯,具有良好到高的对映选择性。在这种情况下,使用联萘环3,3'-位上带有3,5-(CF_3)_2C_6H_3基团的手性磷酸盐对于获得高对映选择性至关重要。3)达尼塞夫斯基二烯与亚胺的环加成反应在手性布朗斯台德酸催化剂的作用下也顺利进行。在这种情况下,2,4,6-三异丙基苯基取代的一个给出了最好的结果。与传统的金属基手性催化剂相反,本发明的布朗斯台德酸不含金属并且在空气中稳定。目前的催化剂为手性有机催化剂添加了新的条目。
项目成果
期刊论文数量(6)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
T.Akiyama, J.Itoh, K.Yokota, K.Fuchibe: "Enantioselective Mannich-type Reaction Catalyzed by a Chiral Bronsted Acid"Angew.Chem.Int.Ed.. 42・12. 1566-1569 (2004)
T.Akiyama、J.Itoh、K.Yokota、K.Fuchibe:“手性布朗斯台德酸催化的对映选择性曼尼希型反应”Angew.Chem.Int.Ed. 42・12(2004)。
- DOI:
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キラルなブレンステッド酸による不斉合成触媒および当該触媒を用いた不斉合成法
使用手性布朗斯台德酸的不对称合成催化剂以及使用该催化剂的不对称合成方法
- DOI:
- 发表时间:2004
- 期刊:
- 影响因子:0
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AKIYAMA Takahiko其他文献
AKIYAMA Takahiko的其他文献
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{{ truncateString('AKIYAMA Takahiko', 18)}}的其他基金
Development of Chiral Bronsted Acid Catalysts
手性布朗斯台德酸催化剂的开发
- 批准号:
19350026 - 财政年份:2007
- 资助金额:
$ 2.5万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of Asymmetric Reactions Catalyzed by Chiral Bronsted Acid
手性布朗斯台德酸催化不对称反应的研究进展
- 批准号:
17550046 - 财政年份:2005
- 资助金额:
$ 2.5万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of Asymmetric Reactions Catalyzed by Bronsted Acid in Aqueous Media
水介质中布朗斯台德酸催化不对称反应的研究进展
- 批准号:
12640528 - 财政年份:2000
- 资助金额:
$ 2.5万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
Development of Asymmetric Allylation Reaction Using Allygermanes
利用烯锗烷开发不对称烯丙基化反应
- 批准号:
10640528 - 财政年份:1998
- 资助金额:
$ 2.5万 - 项目类别:
Grant-in-Aid for Scientific Research (C)
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