1148131-33-2Relevant academic research and scientific papers
A versatile synthetic approach to grandisol monoterpene pheromone
Han, Young Taek,Kim, Nam-Jung,Jung, Jong-Wha,Yun, Hwayoung,Lee, Sujin,Suh, Young-Ger
experimental part, p. 1437 - 1442 (2012/04/23)
A versatile and efficient synthetic procedure for the grandisol pheromone library has been established. The key feature of our synthesis involves a versatile and highly regioselective Pd(0)-catalyzed intramolecular allylic alkylation for the key cyclobutane skeleton of grandisol. In this connection, the concise synthesis of (±)-grandisol as well as mechanism study of Pd(0)-catalyzed regioselective cyclization as a key reaction have also been accomplished.
Formation of carbocycles by intramolecular conjugate displacement: Scopeand mechanistic insights
Wang, Lihong,Prabhudas, Bodhuri,Clive, Derrick L. J.
supporting information; experimental part, p. 6003 - 6012 (2009/09/25)
A detailed study has been made of a method of ring closure categorized as an all-carbon intramolecular conjugate displacement (ICD). This reaction involves intramolecular addition of a carbanion, which is stabilized by at least one electron-withdrawing group, to a Michael acceptor which has a leaving group in an allylic position. The process formally resembles a combination of Michael addition and S N2' displacement. The overall result is formation of a ring with loss of the allylic leaving group and shift of the original double bond to a new location spanning the positions of the electron-withdrawing substituent of the Michael acceptor subunit and the original allylic leaving group. The starting materials are easily prepared by a selenium-based version of the Morita-Baylis-Hillman reaction. The cyclizations are transition metal free and occur under mild conditions, using DBU or Cs 2CO 3 inMeCN or THF. Acetate is a suitable leaving group and the electron-withd rawing substituent of the Michael acceptor unit can be CO 2R,SO 2Ph, or CN. Six- and seven-membered rings are formed effi ciently, and complex structures, such as those resembling the core of CP-225,917, are easily assembled. The products of these ICD reactions are themselves classical Michael acceptors. A range of mechanisms probably operates, depending on the structure of the starting material and the reaction conditions, but conclusive evidence for a stepwise mechanism was obtained in a suitably biased case, while other observations are compatible with a concerted process or a stepwise path involving a short-lived carbanion that evades capture by a proton source.
