Department of Chemistry, University of California, Berkeley, California 94720, United States.
J Am Chem Soc. 2015 May 20;137(19):6327-34. doi: 10.1021/jacs.5b02254. Epub 2015 May 6.
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.
过渡金属介导的 C-C 键活化/断裂方法的不断发展将为实施新的合成策略提供更多机会。我们探索了铑（I）催化的位于羟基化的蒎烯衍生物中环丁醇的 C-C 活化，其以与我们用许多传统亲电试剂观察到的 C-C 键断裂互补的方式进行。机理和计算研究深入了解了 C-H 键活化在 Rh 催化的 C-C 键活化过程中立体化学结果中的作用。使用这种新方法，已经获得了形成天然产物核心的官能化环己烯酮，包括螺吲哚美辛和 phomactin A。
