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Enantioselective Conjugate Addition of Catalytically Generated Zinc Homoenolate
ChemRxiv Pub Date : 2021-01-20
Yoshiya Sekiguchi, Naohiko Yoshikai

We report herein an enantioselective conjugate addition reaction of a zinc homoenolate, catalytically generated via ring opening of a cyclopropanol, to an α,β-unsaturated ketone. The reaction is promoted by a zinc aminoalkoxide catalyst generated from Et2Zn and a chiral β-amino alcohol to afford 1,6- diketones, which undergo, upon heating, intramolecular aldol condensation to furnish highly substituted cyclopentene derivatives with good to high enantioselectivities. The reaction has proved applicable to various 1-substituted cyclopropanols as well as chalcones and related enones. The chiral amino alcohol has proved to enable ligand-accelerated catalysis of the homoenolate generation and its conjugate addition. Positive nonlinear effects and lower reactivity of a racemic catalyst have been observed, which can be attributed to a stable and inactive heterochiral zinc aminoalkoxide dimer.

中文翻译:

催化生成的均烯酸锌的对映选择性共轭加成

我们在此报告了经由环丙醇的开环催化生成的α-β-不饱和酮的均戊烯酸锌的对映选择性共轭加成反应。由Et2Zn和手性β-氨基醇生成的氨基锌醇锌催化剂促进反应,得到1,6-二酮,在加热时,分子内的羟醛缩合反应可提供具有良好至高对映选择性的高度取代的环戊烯衍生物。已证明该反应适用于各种1-取代的环丙醇以及查耳酮和相关的烯酮。已证明手性氨基醇能够实现配体加速的均烯酸酯生成及其偶联物添加的催化。已观察到外消旋催化剂的正非线性效应和较低的反应性,
更新日期:2021-01-20
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