金属/有机双功能催化剂的设计、合成与应用

Metal/Organo bifunctional catalysts consist of metal and organo catalysis modules to activate both of the reactants. Another advantage of this type of catalysts is: both substrates can be pulled together to faciliate the reaction a lot and meanwhile provide better control of the stereoselectivity. At present, known successful bifunctional catalysts dominantly consist of main group metals and early transition metals that function as pure Lewis acids. For metals known as Pi-Lewis acids or metals that exhibit oxidation/reduction properties as catalysts, like gold, platinium, palladium and rhodium etc., only a few examples were reported. The examples of asymmetric catalysis are even more scarce and thus in high demand. In this project, we will design and synthesize a series of new bifunctional catalysts based on amino acids and BINOL skeleton and try to apply them in reactions includng:asymmetric α-allylation of carbonyls;rhodium catalyzed asymmetric alkylation reaction between ketones and alkenes. A series of gold/Lewis base catalysts will be synthesized based on biphenyl skeleton and employed for the intermolecular hydrosilyloxylation reaction and subsequent tandem reaction.

金属/有机双功能催化剂含有金属和有机两种催化模块，能够同时对两种反应物进行活化的催化剂。这类催化剂另一种优势在于通过拉近两种反应中间体的空间位置，带来反应速率的巨大提升，同时更好地控制反应的立体选择性。现有的金属/有机双功能催化剂主要集中在前过渡金属与主族金属，主要是应用金属的路易斯酸性。而对于能活化π键的金属或催化过程涉及氧化还原的金属，如金、铂、钯、铑等，仅有少数几例，其中不对称催化的例子更加少见。本项目将基于氨基酸骨架、BINOL骨架等设计一系列新型双功能配体，并将其应用于羰基化合物的不对称α位烯丙基化反应、铑催化的酮与烯烃的反应等。基于联苯骨架合成一类金/路易斯碱双功能催化剂，尝试实现硅醇对炔烃的分子间加成反应，并应用于不对称串联反应。

本项目主要致力于利用多功能催化剂实现不对称串联反应，取得了一些有特色的研究成果，主要包括：（1）多功能手性二价钯催化的碳-氢活化/不对称烯丙基化串联反应；（2）利用多功能钯/贫电子亚磷酰胺配体催化合成手性杂环化合物；（3）Rh/有机小分子不对称串联催化烯烃的不对称分子间氢氨甲基化反应；（4）利用多催化剂体系实现氢甲酰化/不对称烯丙基化串联反应等。. 项目执行期间，共发表学术论文14篇，其中包括Chem 1篇、J. Am. Chem. Soc.1篇、Angew. Chem. Int. Ed. 2篇、ACS Catal. 1篇、Org. Lett. 6篇，多篇论文被Synfacts、《有机化学》等作亮点评论。