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Phosphoramidite-Rhodium Complexes as Catalysts for the Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates and
Rebecca Keller Friedman1, Kevin M Oberg, Derek M Dalton
1Colorado State University, Fort Collins CO, 80523.
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.
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