Abstract:

The continued development of transition-metal-mediated C−C bond activation/cleavage methods would provide even more opportunities to implement novel synthetic strategies. We have explored the Rh(I)-catalyzed C−C activation of cyclobutanols resident in hydroxylated derivatives of pinene, which proceed in a complementary manner to the C−C bond cleavage that we have observed with many traditional electrophilic reagents. Mechanistic and computational studies have provided insight into the role of C−H bond activation in the stereochemical outcome of the Rh-catalyzed C−C bond activation process. Using this new approach, functionalized cyclohexenones that form the cores of natural products, including the spiroindicumides and phomactin A, have been accessed.

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