Phosphoramidite-Rhodium Complexes as Catalysts for the Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates and Alkynes.
Phosphoramidite-Rhodium Complexes as Catalysts for the Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates and Alkynes.
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DOI：
10.1351/pac-con-09-12-09
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发表时间：
2009-07-01
期刊：
影响因子：
--
通讯作者：
Rovis T
中科院分区：
文献类型：
--
作者：
Friedman RK;Oberg KM;Dalton DM;Rovis T
介绍了铑催化异氰酸烯基酯和外源炔的不对称[2+2+2]环加成反应形成中氮茚酮和喹嗪酮骨架的发现和发展。这种方法已经扩展到包括取代的烯烃和二烯，各种空间和电子上不同的炔，和取代异氰酸酯的双酰亚胺。通过X-射线分析Rh（COD）/亚磷酰胺配合物，添加剂，修改对映体确定步骤，和其他实验数据，已提出一种机制，解释内酰胺，乙烯基乙酰胺，吡啶酮产品及其形成的因素。最后，我们将该方法应用于（+）-lasubine-II和（-）-209D的合成。
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.