The Molecular Design of Chiral Crown Ethers as Efficient Asymmetric Catalysts.

作为高效不对称催化剂的手性冠醚的分子设计。

• 批准号: 02557085
• 负责人: KOGA Kenji
• 金额: $ 4.54万
• 依托单位: University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02557085/
• 关键词: Chiral Crown Ethers; Chiral Complexes; Catalytic Asymmetric Reactions; Enantioselective Reactions; Michael Reactions; エナンチオ面選択反応

The design of efficient catalysts for asymmetric reactions has been a recent focus in synthetic organic chemistry.Crown ethers are anticipated to be efficient catalysts for C-C bond formations, because they have been proved to complex with metal cations and activate counteranions.The asymmtric Michael, - addition of methyl phenylthioacetate 2 to 2 - cyclohexenone 3 is a good reaction to obtain optically active delta - ketoester derivative (4). The optical purity of C-3 position of 4 was determined by conversion of 4 to 5, the reductive desul-furization with (nBu)_4 SnH in a good yield. We have found that C_2-svmmetric 1 complexed with KOtBu (10mol%) catalyzes the Michael reaction of 2 and induces the relatively high enantioselectivity(71%e. e. S).

有效催化剂的不对称反应的设计已成为合成有机化学的最新重点。预计c -c -C键形成的crown污染剂被预计是有效的催化剂，因为它们已被证明是与金属阳离子相复杂的，并激活了反趋势，并激活了反趋化。酮酯衍生物（4）。 C-3位置的光学纯度通过4至5的转换确定，即与（NBU）_4 SNH的还原性抗化，以良好的产率。我们发现，C_2-SVMmetric 1与Kotbu（10mol％）复合催化2的迈克尔反应并诱导相对较高的对映选择性（71％e。e。S）。

项目成果

S. Aoki, S. Sasaki, and K. Koga: "Asymmetric Michael Addition Reactions of Methyl Phenylthioacetate t+ 2 - cyclopentenone Catalyzed by Chiral Crown - KOtBu Complexes." Heterocycles. 33. (1992)

S. Aoki、S. Sasaki 和 K. Koga：“手性冠 - KOtBu 配合物催化的苯基硫代乙酸甲酯 t 2 - 环戊烯酮的不对称迈克尔加成反应”。

S.Aoki,S.Sasaki,and K.Koga: "Simple Chiral Crown Ethers Complexed with Potassium test-Butoxide as Efficient Catalyst for Asymmetric Michael Additions" Tetrahedron Letters. 30. 7229-7230 (1989)

S.Aoki、S.Sasaki 和 K.Koga：“简单手性冠醚与测试丁醇钾络合作为不对称迈克尔加成的有效催化剂”四面体字母。