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Unexpected Propargylic Retro-Brook Rearrangements in Alkynes.
Wang, Xiao; Gao, Qi; Buevich, Alexei V; Yasuda, Nobuyoshi; Zhang, Yonglian; Yang, Rong-Sheng; Zhang, Li-Kang; Martin, Gary E; Williamson, R Thomas.
Afiliación
  • Wang X; Analytical Research and Development (Rahway) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Gao Q; Analytical Research and Development (Kenilworth) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Buevich AV; Analytical Research and Development (Kenilworth) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Yasuda N; Department of Discovery Chemistry (Kenilworth) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Zhang Y; Department of Discovery Chemistry (Kenilworth) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Yang RS; Analytical Research and Development (Kenilworth) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Zhang LK; Analytical Research and Development (Kenilworth) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Martin GE; Analytical Research and Development (Rahway) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
  • Williamson RT; Analytical Research and Development (Rahway) , Merck & Co., Inc. , Kenilworth , New Jersey 07033 , United States.
J Org Chem ; 84(16): 10024-10031, 2019 08 16.
Article en En | MEDLINE | ID: mdl-31283876
Retro-Brook rearrangements refer to the intramolecular migration of a silyl group from oxygen to carbon. In this study, we report a novel propargylic retro-Brook rearrangement observed in terminal alkynes bearing a silyl ether moiety. Retro-Brook rearrangements involving [1,2]-, [1,4]-, and [1,5]-migrations are described, affording propargylsilanes in reasonable yield. The reaction mechanism was investigated experimentally by deuterium quenching and rationalized by density functional theory calculations. The terminal alkyne and the subsequent propargyl/allenyl dianion were shown to be crucial for the reaction favoring the retro-Brook rearrangement product over the Brook rearrangement. The second deprotonation at the propargylic position was determined to be the rate-limiting step. In addition, a gas-phase Brook-type rearrangement of the propargylsilanes was observed under GC-MS conditions. This observation was also further confirmed by DFT calculations.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Org Chem Año: 2019 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Org Chem Año: 2019 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos