title: Highly enantioselective rhodium(I)-catalyzed activation of enantiotopic cyclobutanone C-C bonds.
abstract: The selective functionalization of carbon-carbon σ bonds is a synthetic strategy that offers uncommon retrosynthetic disconnections. Despite progress in C-C activation and its great importance, the development of asymmetric reactions lags behind. Rhodium(I)-catalyzed selective oxidative additions into enantiotopic C-C bonds in cyclobutanones are reported. Even operating at a reaction temperature of 130 °C, the process is characterized by outstanding enantioselectivity with the e.r. generally greater than 99.5:0.5. The intermediate rhodacycle is shown to react with a wide variety of tethered olefins to deliver complex bicyclic ketones in high yields.
authors: Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa.
authors: Laetitia
authors: L
authors: Souillart
authors: Evelyne
authors: E
authors: Parker
authors: Nicolai
authors: N
authors: Cramer
keywords: CC activation; asymmetric catalysis; cyclobutanone; rearrangement; rhodium