Novel carbohydrate olefin hybrid ligands in rhodium catalyzed reactions: Challenging substrates in 1,4-additions

铑催化反应中的新型碳水化合物烯烃杂化配体：1,4-加成中具有挑战性的底物

• 批准号: 201268350
• 负责人: Professor Dr. Holger Butenschön
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/201268350?language=en
• 关键词: Novel; carbohydrate; olefin; hybrid; ligands

In the first funding period a number of new chiral heterobidendate ligands with an alkene and a phosphite moiety were prepared based on carbohydrates from the chiral pool. These ligands are well accessible, pseudo-enatiomeric hybrid ligands, which were successfully employed in asymmetric rhodium-catalyzed 1,4-additions. Here we plan to investigate in detail asymmetric catalytic 1,4-additions with challenging nucleophiles such as heteroarylboronates by NMR spectroscopy in order to identify and solve occurring problems. Further, problematic electrophiles such as cycloalkenes with an exocyclic acceptor substituent, e. g. cycloalkene-1-carbonitriles, will be employed in the reaction. On this basis the synthesis of various medicinal drugs, e. g. (-)-paroxenine, will be achieved. In addition, the so far unprecedented asymmetric catalytic 1,4-addition at C2-substituted cyclopentenes will be investigated for synthesizing the steroid hormone equilenine. 1,4-Additions at 1,3-dioxin-4-one are unknown and will be scrutinized as a new access to 3-hydroxycarbonyl compounds. Finally orienting experiments with a combination of the two project lines will be undertaken.

在第一个资助期，以手性池中的碳水化合物为基础，制备了一些新的具有烯烃和亚磷酸酯部分的手性杂交酯配体。这些配体是易于接近的伪对映体杂化配体，已成功地应用于不对称铑催化的1,4-加成反应中。在这里，我们计划通过核磁共振光谱详细研究具有挑战性的亲核试剂如杂芳基硼酸盐的不对称催化1,4-加成，以识别和解决发生的问题。此外，有问题的亲电试剂，如具有外环受体取代基的环烯烃，如环烯烃-1-碳腈，将用于反应中。在此基础上，可以合成各种药物，如(-)-帕罗西宁。此外，还将研究迄今为止尚未出现的在c2取代环戊烯上的不对称催化1,4加成反应，以合成类固醇激素马烯。1,4- 1,3-二恶英-4- 1的添加是未知的，将作为3-羟基羰基化合物的新途径进行审查。最后，将结合两个项目线进行定向实验。