1097189-54-2Relevant academic research and scientific papers
Enantioselective 1,2-Anionotropic Rearrangement of Acylsilane through a Bisguanidinium Silicate Ion Pair
Cao, Weidi,Tan, Davin,Lee, Richmond,Tan, Choon-Hong
supporting information, p. 1952 - 1955 (2018/02/17)
Highly enantioselective bisguanidinium-catalyzed tandem rearrangements of acylsilanes are reported. The acylsilanes were activated via an addition of fluoride on the silicon to form a penta-coordinate anionic silicate intermediate. The silicate then underwent alkyl or aryl group migration from the silicon atom to the neighboring carbonyl carbon atom (1,2-anionotropic rearrangement), followed by [1,2]-Brook rearrangement to provide the secondary alcohols in high yields with excellent enantioselectivities (up to 95% ee). The isolation of an α-silylcarbinol intermediate as well as DFT calculations revealed that the 1,2-anionotropic rearrangement occurred via a bisguanidinium silicate ion pair, which is the stereodetermining step. The chiral center formed is then retained without inversion through the subsequent [1,2]-Brook rearrangement. Crotyl acylsilanes were smoothly transformed into homoallylic linear crotyl alcohols with retention of E/Z geometry, and no branched alcohols were detected. This clearly suggested that the 1,2-anionotropic rearrangement occurred through a three-membered instead of a five-membered transition state.
Towards bis(acylsilanes) and cyclic unsaturated acylsilanes via metathesis: an exploratory study
Hammaecher, Catherine,Bouillon, Jean-Philippe,Portella, Charles
experimental part, p. 5527 - 5534 (2009/12/03)
New acyl(allyl)- and acyl(vinyl)silanes have been synthesized in order to explore cross metathesis or ring-closing metathesis as a new way towards bis(acyl)silanes or unsaturated cyclic acylsilanes, respectively. Metathesis from acylsilanes did not work b
New 6-oxa-2-silabicyclo[2.2.0]hexanes by photochemical conversion of acyl(allyl)(dimethyl)silanes
Hammaecher, Catherine,Portella, Charles
supporting information; scheme or table, p. 5833 - 5835 (2009/04/13)
Under UV irradiation in acetonitrile, acyl(allyl)silanes undergo an intramolecular (2+2) cycloaddition (Paterno-Buechi type reaction) to give unprecedented 1-alkyl-6-oxa-2-silabicyclo[2.2.0] hexanes. The Royal Society of Chemistry.
