亚磷酰胺-铑配合物作为异氰酸烯酯和炔烃不对称[2+2+2]环加成反应的催化剂
Phosphoramidite-Rhodium Complexes as Catalysts for the Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates and Alkynes.
作者信息
Friedman Rebecca Keller, Oberg Kevin M, Dalton Derek M, Rovis Tomislav
机构信息
Colorado State University, Fort Collins CO, 80523.
出版信息
Pure Appl Chem. 2009 Jul 1;82(7):1353-1364. doi: 10.1351/PAC-CON-09-12-09.
Abstract
The discovery and development of the asymmetric rhodium-catalyzed [2+2+2] cycloaddition of alkenyl isocyanates and exogenous alkynes to form indolizinone and quinolizinone scaffolds is described. This methodology has been expanded to include substituted alkenes and dienes, a variety of sterically and electronically diverse alkynes, and carbodiimides in place of the isocyanate. Through X-ray analysis of Rh(cod)/phosphoramidite complexes, additives that modify the enantio-determining step, and other experimental data, a mechanism has been proposed that explains lactam, vinylogous amide, and pyridone products and the factors governing their formation. Finally, we have applied this methodology to the synthesis of (+)-lasubine-II and (-)-209D.
摘要
本文描述了不对称铑催化的烯基异氰酸酯与外源炔烃进行[2+2+2]环加成反应以形成中氮茚酮和喹嗪酮骨架的发现与发展。该方法已扩展至包括取代烯烃和二烯、各种空间和电子性质不同的炔烃以及用碳二亚胺代替异氰酸酯的情况。通过对Rh(cod)/亚磷酰胺配合物的X射线分析、修饰对映体决定步骤的添加剂以及其他实验数据，提出了一种机制，该机制解释了内酰胺、烯醇酰胺和吡啶酮产物及其形成的影响因素。最后，我们将该方法应用于(+)-拉苏宾-II和(-)-209D的合成。
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