64299-60-1Relevant academic research and scientific papers
Silylation-desilylation of propargyl amides: rapid synthesis of functionalised aldehydes and β-lactams
Aronica, Laura Antonella,Valentini, Giulia,Caporusso, Anna Maria,Salvadori, Piero
, p. 6843 - 6854 (2008/02/07)
Propargyl functionalised β-silylalkenals were easily prepared starting from suitable propargyl compounds by a silylformylation process. In particular the use of propargyl tosyl amides allowed the synthesis of α,β-unsaturated aldehydes through a two-step sequence of silylformylation-desilylation reactions. TBAF was employed to induce the desilylation process that was performed under very mild experimental conditions and occurred along with an elimination step of the tosylamido moiety affording 2-methylaryl-2-alkenals with good yields and stereoselectivity. When the tosyl amides were reacted with a hydrosilane in the presence of catalytic amounts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) α-silylmethylene-β-lactams were synthesised through a silylcarbocyclisation process. A high chemoselectivity towards the β-lactam was observed when dialkyl propargyl amides were employed. The obtained β-lactams were easily transformed into the corresponding methylaryl-β-lactams by fluoride induced aryl migration-desilylation with total retention of configuration of the migrating group and complete stereoselectivity towards the more stable β-lactam (E)-isomer.
Silylformylation-desilylation of propargyl amides: Synthesis of α,β-unsaturated aldehydes
Aronica, Laura Antonella,Raffa, Patrizio,Valentini, Giulia,Caporusso, Anna Maria,Salvadori, Piero
, p. 527 - 530 (2007/10/03)
α,β-Unsaturated aldehydes are prepared from easily available propargyl amides through a two-step sequence of silylformylation-desilylation reactions. The substituent on the nitrogen atom markedly influences both reactions, β-silylalkenals being formed in
Development of an anomalous heck reaction: Skeletal rearrangement of divinyl and enyne carbinols
Ndungu, J. Maina,Larson, Kimberly K.,Sarpong, Richmond
, p. 5845 - 5848 (2007/10/03)
(Chemical Equation Presented) A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress β-hydride elimination of organopalladium intermediates appears to be critical to the success of these processes.
