Berthon-Gelloz, Guillaume
Marchant, Mélanie
Straub, Bernd F
Marko, Istvan
[UCL]
Alkenyl silanes are efficiently converted to the corresponding silyl cyclopropanes in the presence of a slight excess of diazomethane (2-4 equiv) and a low loading of Pd(OAc)(2) (<0.5 mol %). Diazoethane and diazobutane can also be employed and yield silyl cyclopropanes with diastereoselectivities of up to 10:1 for the trans isomer. When conducted on a 4 g scale, the reaction only required a catalyst loading of 5x10(-3) mol %, which corresponds to a turnover frequency of 40 000 h(-1). Competition experiments revealed that vinyl silanes can be selectively cyclopropanated in the presence of an aliphatic terminal alkene and styrene. The complex [Pd(0) (2)(DVTMS)(3)] (38, DVTMS=divinyltetramethyldisiloxane) proved to be an exceptionally active catalyst for the cyclopropanation reaction, giving complete conversion at -35 degrees C in 1 min. Intermolecular and intramolecular competition experiments with DVTMS (36), both with Pd(OAc)(2) and 38, provided strong evidence for a Pd(0)(alkenyl silane)(3) resting state. Detailed density functional calculations on the reaction pathways for the cyclopropanation of trimethylvinylsilane and DVTMS by diazomethane with Pd(0) corroborated the experimental observations.
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Bibliographic reference |
Berthon-Gelloz, Guillaume ; Marchant, Mélanie ; Straub, Bernd F ; Marko, Istvan. Palladium-Catalyzed Cyclopropanation of Alkenyl Silanes by Diazo Alkanes: Evidence for a Pd(0) Mechanism.. In: Chemistry - A European Journal, Vol. 15, no. 12, p. 2923-31 (2009) |
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http://hdl.handle.net/2078.1/21413 |