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Mechanistic insight into the (NHC)copper(I)-catalyzed hydrosilylation of ketones

(2014) ORGANOMETALLICS. 33(8). p.1953-1963
Author
Organization
Abstract
(NHC)copper(I) hydride catalyzed ketone hydrosilylation is an efficient method for the enantioselective synthesis of secondary alcohols. Herein, we represent a computational study of this reaction using density functional theory (DFT) on realistic model systems. This study is supported by kinetic investigations, using in situ FTIR measurements. The calculations validate the previously proposed reaction mechanism and explain the high activity of (ORI)(x)(R3-xSi)-Si-2-H types of silanes. Experimental evidence in favor of the monomeric (NHC)CuH form of the catalyst is also given. Combining experimental and theoretical results furthermore highlights a Lewis base activation of the hydrosilane, leading to a modified suggestion for the mechanistic scheme of the catalytic cycle.
Keywords
CATALYZED ASYMMETRIC HYDROSILYLATION, EFFICIENT ENANTIOSELECTIVE HYDROSILYLATION, TRANSITION-METAL-COMPLEXES, EFFECTIVE CORE POTENTIALS, HETEROCYCLIC-CARBENE NHC, CARBONYL-COMPOUNDS, BASIS-SETS, COPPER FLUORIDE, ARYL-ALKYL, MOLECULAR CALCULATIONS

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Chicago
Vergote, Thomas, Fady Nahra, Alain Merschaert, Olivier Riant, Daniel Peeters, and Tom Leyssens. 2014. “Mechanistic Insight into the (NHC)copper(I)-catalyzed Hydrosilylation of Ketones.” Organometallics 33 (8): 1953–1963.
APA
Vergote, T., Nahra, F., Merschaert, A., Riant, O., Peeters, D., & Leyssens, T. (2014). Mechanistic insight into the (NHC)copper(I)-catalyzed hydrosilylation of ketones. ORGANOMETALLICS, 33(8), 1953–1963.
Vancouver
1.
Vergote T, Nahra F, Merschaert A, Riant O, Peeters D, Leyssens T. Mechanistic insight into the (NHC)copper(I)-catalyzed hydrosilylation of ketones. ORGANOMETALLICS. 2014;33(8):1953–63.
MLA
Vergote, Thomas et al. “Mechanistic Insight into the (NHC)copper(I)-catalyzed Hydrosilylation of Ketones.” ORGANOMETALLICS 33.8 (2014): 1953–1963. Print.
@article{8586442,
  abstract     = {(NHC)copper(I) hydride catalyzed ketone hydrosilylation is an efficient method for the enantioselective synthesis of secondary alcohols. Herein, we represent a computational study of this reaction using density functional theory (DFT) on realistic model systems. This study is supported by kinetic investigations, using in situ FTIR measurements. The calculations validate the previously proposed reaction mechanism and explain the high activity of (ORI)(x)(R3-xSi)-Si-2-H types of silanes. Experimental evidence in favor of the monomeric (NHC)CuH form of the catalyst is also given. Combining experimental and theoretical results furthermore highlights a Lewis base activation of the hydrosilane, leading to a modified suggestion for the mechanistic scheme of the catalytic cycle.},
  author       = {Vergote, Thomas and Nahra, Fady and Merschaert, Alain and Riant, Olivier and Peeters, Daniel and Leyssens, Tom},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {CATALYZED ASYMMETRIC HYDROSILYLATION,EFFICIENT ENANTIOSELECTIVE HYDROSILYLATION,TRANSITION-METAL-COMPLEXES,EFFECTIVE CORE POTENTIALS,HETEROCYCLIC-CARBENE NHC,CARBONYL-COMPOUNDS,BASIS-SETS,COPPER FLUORIDE,ARYL-ALKYL,MOLECULAR CALCULATIONS},
  language     = {eng},
  number       = {8},
  pages        = {1953--1963},
  title        = {Mechanistic insight into the (NHC)copper(I)-catalyzed hydrosilylation of ketones},
  url          = {http://dx.doi.org/10.1021/om401097q},
  volume       = {33},
  year         = {2014},
}

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