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Selectivity switch in the synthesis of vinylgold(I) intermediates

(2011) ORGANOMETALLICS. 30(22). p.6328-6337
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Abstract
An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)](+) species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)](+) species with "classical" pi activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Bronsted character of [Au(IPr)(OH)). Mechanistic and DFT studies support the mechanistic hypotheses.
Keywords
HOMOGENEOUS GOLD CATALYSIS, N-HETEROCYCLIC CARBENE, C-H BONDS, STRUCTURAL-CHARACTERIZATION, PLATINUM CATALYSIS, SOLUTION BEHAVIOR, COMPLEXES, ALKYNES, HYDROAMINATION, ALLENES

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Chicago
Hashmi, A Stephen K, Andreas M Schuster, Sylvain Gaillard, Luigi Cavallo, Albert Poater, and Steven Nolan. 2011. “Selectivity Switch in the Synthesis of vinylgold(I) Intermediates.” Organometallics 30 (22): 6328–6337.
APA
Hashmi, A. S. K., Schuster, A. M., Gaillard, S., Cavallo, L., Poater, A., & Nolan, S. (2011). Selectivity switch in the synthesis of vinylgold(I) intermediates. ORGANOMETALLICS, 30(22), 6328–6337.
Vancouver
1.
Hashmi ASK, Schuster AM, Gaillard S, Cavallo L, Poater A, Nolan S. Selectivity switch in the synthesis of vinylgold(I) intermediates. ORGANOMETALLICS. 2011;30(22):6328–37.
MLA
Hashmi, A Stephen K et al. “Selectivity Switch in the Synthesis of vinylgold(I) Intermediates.” ORGANOMETALLICS 30.22 (2011): 6328–6337. Print.
@article{8168988,
  abstract     = {An unexpected regioselectivity reversal was observed in the synthesis of vinylgold(I) complexes from propargyl carboxamides. The use of [Au(IPr)(OH)] affords preferentially vinylgold(I) complexes resulting from a 5-exo-dig cyclization, whereas the use [Au(IPr)](+) species, generated in situ starting from [Au(IPr)(Cl)] and AgOTf, leads to vinylgold(I) complexes which form via a 6-endo-dig cyclization, This unexpected "selectivity switch" for this cyclization led us to propose two different reaction pathways enabling the formation of the two different products. One mechanism involves the [Au(IPr)](+) species with "classical" pi activation of the alkyne framework of the carboxamides, and the second represents an "unusual" use of the basic Bronsted character of [Au(IPr)(OH)). Mechanistic and DFT studies support the mechanistic hypotheses.},
  author       = {Hashmi, A Stephen K and Schuster, Andreas M and Gaillard, Sylvain and Cavallo, Luigi and Poater, Albert and Nolan, Steven},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {HOMOGENEOUS GOLD CATALYSIS,N-HETEROCYCLIC CARBENE,C-H BONDS,STRUCTURAL-CHARACTERIZATION,PLATINUM CATALYSIS,SOLUTION BEHAVIOR,COMPLEXES,ALKYNES,HYDROAMINATION,ALLENES},
  language     = {eng},
  number       = {22},
  pages        = {6328--6337},
  title        = {Selectivity switch in the synthesis of vinylgold(I) intermediates},
  url          = {http://dx.doi.org/10.1021/om2009556},
  volume       = {30},
  year         = {2011},
}

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