Stereoselective rhodium-catalyzed 2-C-H 1,3-dienylation of indoles: dual functions of the directing group

A rhodium-catalyzed intermolecular highly stereoselective 1,3-dienylation at the 2-position of indoles with non-terminal allenyl carbonates has been developed by using 2-pyrimidinyl or pyridinyl as the directing group. The reaction tolerates many functional groups affording the products in decent yields under mild conditions. In addition to C-H bond activation, the directing group also played a vital role in the determination of Z-stereoselectivity for the C-H functionalization reaction with 4-aryl-2,3-allenyl carbonates, which is confirmed by the E-selectivity observed with 4-alkyl-2,3-allenyl carbonates. DFT calculations have been conducted to reveal that pi-pi stacking involving the directing 2-pyrimidinyl or pyridinyl group is the origin of the observed stereoselectivity. Various synthetic transformations have also been demonstrated.