Silylene transfer reactions are powerful transformations that allow for stereospecific and stereoselective carbon-carbon bond formations. Silver-catalyzed silylene transfer to divinyl ketones followed by treatment with a dienophile allows for the rapid construction of highly functionalized cyclohexenes diastereoselectively. This two-step, one-pot reaction allows for rapid entry into highly substituted cyclohexenes that could serve as intermediates in the synthesis of biologically-active natural products. Preliminary studies suggest that the metal catalyst is more intimately involved in the silylene transfer than previously theorized. Thus, chiral ligands on the metal catalyst carries the potential to allow enantioselective silylene transfer. The addition of chiral ligands would allow for the transformation to, not only be diastereoselctive, but enantioselective as well. In this way, the synthesis of natural products could be achieved with enantiocontrol. The isolation of complex biologically active natural products from the organisms that produce them is rarely feasable. Biological studies of such compounds could be very expensive depending on the method of isolaton or the organism from which they are isolated. It is the organic chemist's job to devise ways to synthesize these products so they are more cost effective to study and potentially be used for medical treatment. ? ? ?
| Ventocilla, Christian C; Woerpel, K A (2012) Synthesis of silyloxy dienes by silylene transfer to divinyl ketones: application to the asymmetric synthesis of substituted cyclohexanes. J Org Chem 77:3277-83 |
| Ventocilla, Christian C; Woerpel, K A (2011) Silylene-mediated polarity reversal of dienoates: additions of dienoates to aldehydes at the ?-position to form trans-dioxasilacyclononenes. J Am Chem Soc 133:406-8 |
