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手性联萘金（I）配合物催化氮杂环丙烷与烯烃的 1,3-偶极环加成反应的合成范围和密度泛函理论分析。

Synthetic scope and DFT analysis of the chiral binap-gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes.

机构信息

Departamento de Química Orgánica e Instituto de Síntesis Orgánica, Universidad de Alicante, Apdo. 99, 03080-Alicante, Spain.

Departamento de Química Orgánica I, Facultad de Química, Universidad del País Vasco, Apdo. 1072, E-20018 San Sebastián, Spain.

出版信息

Beilstein J Org Chem. 2013 Nov 11;9:2422-33. doi: 10.3762/bjoc.9.280. eCollection 2013.

DOI:10.3762/bjoc.9.280
PMID:24367409
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3869218/
Abstract

The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(S a)-Binap·AuTFA]2. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

摘要

(S)-BINAP·AuTFA]2 二聚手性配合物高效催化甘氨酸衍生的氮丙啶酮与马来酰亚胺的 1,3-偶极环加成反应。而丙氨酸衍生的恶唑啉酮仅与叔丁基丙烯酸酯反应，表现出异常的区域化学选择性，这一现象通过自然共振理论和核独立化学位移计算得到了解释和支持。使用在 M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF)水平上计算的密度泛函理论（DFT），分析了手性配合物对马来酰亚胺和叔丁基丙烯酸酯高对映选择性的起源。描述了这些环加成产物在合成具有 2,5-反式排列的新型脯氨酸衍生物和制备复杂稠合多环分子中的几种应用。

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