Transition Metal Lewis Acids as Chiral Catalysts: Mechanistic and Synthetic Studies

过渡金属路易斯酸作为手性催化剂：机理和合成研究

• 批准号: 136477835
• 负责人: Dr. Bettina Bressel
• 金额: --
• 依托单位: Département de Chimie Organique
• 依托单位国家: 德国
• 项目类别: Research Fellowships
• 财政年份: 2009
• 资助国家: 德国
• 起止时间: 2008-12-31 至 2009-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/136477835?language=en
• 关键词: Transition; Metal; Lewis; Acids; Chiral

The development and application of chiral catalysts for asymmetric synthesis is of enormous interest for economical and ecological reasons. Biologically active chiral molecules can be synthesized without using stoichiometric amounts of optically pure compounds. Very good results for cycloaddition reactions with α,β unsaturated aldehydes have been obtained with remarkably stable and recoverable rutheniumbased Lewis acids bearing chiral perfluoroaryldiphosphinite ligands. Diels-Alder reactions were also successfully applied to α,β unsaturated ketones. This project aims at an understanding of mechanistic details of the catalysis and to develop further applications. Encouraged by preliminary results with α,β unsaturated ketones, the synthetic potential of these catalysts will be extended to conjugated addition reactions. A challenging aim is to apply α,β unsaturated aldehydes for Mukaiyama-Michael additions, as only one organocatalytic approach has been reported in this area. Furthermore, the versatility of the catalyst will be tested by performing reactions not involving coordination of a carbonyl compound. These are for example diastereo and enantioselective catalytic cyclopropanations and aziridinations.

手性催化剂在不对称合成中的开发和应用，无论是在经济上还是在生态上，都引起了人们极大的兴趣。生物活性手性分子可以在不使用化学计量的光学纯化合物的情况下合成。用带有手性全氟芳基二次膦酸酯配体的具有显著稳定性和可回收性的季铵盐基刘易斯酸与α，β不饱和醛的环加成反应获得了非常好的结果。Diels-Alder反应也被成功地应用于α，β不饱和酮。该项目旨在了解催化的机理细节，并开发进一步的应用。受α，β不饱和酮的初步结果的鼓舞，这些催化剂的合成潜力将扩展到共轭加成反应。一个具有挑战性的目标是将α，β不饱和醛用于Mukaiyama-Michael加成，因为在该领域中仅报道了一种有机催化方法。此外，催化剂的多功能性将通过进行不涉及羰基化合物配位的反应来测试。这些是例如非对映和对映选择性催化环丙烷化和氮丙啶化。