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N-Heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation

(2012) ACCOUNTS OF CHEMICAL RESEARCH. 45(6). p.778-787
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Abstract
Environmental concerns have and will continue to have a significant role in determining how chemistry is carried out Chemists will be challenged to develop new, efficient synthetic processes that have the fewest possible steps leading to a target molecule, the goal being to decrease the amount of waste generated and reduce energy use. Along this path, chemists will need to develop highly selective reactions with atom-economical pathways producing nontoxic byproduct. In this context, C-H bond activation and functionalization is an extremely attractive method. Indeed, for most organic transformations, the presence of a reactive functionality is required. In Total Synthesis, the "protection and deprotection" approach with such reactive groups limits the overall yield of the synthesis, involves the generation of significant chemical waste, costs energy, and in the end is not as green as one would hope. In turn, if a C-H bond functionalization were possible, instead of the use of a prefunctionalized version of the said C-H bond, the number of steps in a synthesis would obviously be reduced. In this case, the C-H bond can be viewed as a dormant functional group that can be activated when necessary during the synthetic strategy. One issue increasing the challenge of such a desired reaction is selectivity. The deavage of a C-H bond (bond dissociation requires between 85 and 105 kcal/mol) necessitates a high-energy species, which could quickly become a drawback for the control of chemo-, regio-, and stereoselectivity. Transition metal catalysts are useful reagents for surmounting this problem; they can decrease the kinetic barrier of the reaction yet retain control over selectivity. Transition metal complexes also offer important versatility in having distinct pathways that can lead to activation of the C-H bond. An oxidative addition of the metal in the C-H bond, and a base-assisted metal carbon bond formation in which the base can be coordinated (or not) to the metal complexes are possible. These different C-H bond activation modes provide chemists with several synthetic options. In this Account, we discuss recent discoveries involving the versatile NHC-gold(I) and NHC-copper(1) hydroxide complexes (where NHC is N-heterocyclic carbene) showing interesting Bronsted basic properties for C-H bond activation or C-H bond functionalization purposes. The simple and easy synthesis of these two complexes involves their halide-bearing relatives reacting with simple alkali metal hydroxides. These complexes can react cleanly with organic compounds bearing protons with compatible pK(a) values, producing only water as byproduct. It is a very simple protocol indeed and may be sold as a C-H bond activation, although the less flashy "metalation reaction" also accurately describes the process. The synthesis of these complexes has led us to develop new organometallic chemistry and catalysis involving C-H bond activation (metalation) and subsequent C-H bond functionalization. We further highlight applications with these reactions, in areas such as photoluminescence and biological activities of NHC gold(I) and NHC copper(1) complexes.
Keywords
CARBON-HYDROGEN-BONDS, METAL-COMPLEXES, HYDROSILYLATION REACTIONS, ORGANOGOLD COMPOUNDS, CATALYZED REACTIONS, COUPLING REACTIONS, NHC COMPLEXES, FUNCTIONALIZATION, CARBOXYLATION, SILVER

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Chicago
Gaillard, Sylvain, Catherine Cazin, and Steven Nolan. 2012. “N-Heterocyclic Carbene gold(I) and copper(I) Complexes in C-H Bond Activation.” Accounts of Chemical Research 45 (6): 778–787.
APA
Gaillard, S., Cazin, C., & Nolan, S. (2012). N-Heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation. ACCOUNTS OF CHEMICAL RESEARCH, 45(6), 778–787.
Vancouver
1.
Gaillard S, Cazin C, Nolan S. N-Heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation. ACCOUNTS OF CHEMICAL RESEARCH. 2012;45(6):778–87.
MLA
Gaillard, Sylvain, Catherine Cazin, and Steven Nolan. “N-Heterocyclic Carbene gold(I) and copper(I) Complexes in C-H Bond Activation.” ACCOUNTS OF CHEMICAL RESEARCH 45.6 (2012): 778–787. Print.
@article{8168888,
  abstract     = {Environmental concerns have and will continue to have a significant role in determining how chemistry is carried out Chemists will be challenged to develop new, efficient synthetic processes that have the fewest possible steps leading to a target molecule, the goal being to decrease the amount of waste generated and reduce energy use. Along this path, chemists will need to develop highly selective reactions with atom-economical pathways producing nontoxic byproduct. 
In this context, C-H bond activation and functionalization is an extremely attractive method. Indeed, for most organic transformations, the presence of a reactive functionality is required. In Total Synthesis, the "protection and deprotection" approach with such reactive groups limits the overall yield of the synthesis, involves the generation of significant chemical waste, costs energy, and in the end is not as green as one would hope. In turn, if a C-H bond functionalization were possible, instead of the use of a prefunctionalized version of the said C-H bond, the number of steps in a synthesis would obviously be reduced. In this case, the C-H bond can be viewed as a dormant functional group that can be activated when necessary during the synthetic strategy. 
One issue increasing the challenge of such a desired reaction is selectivity. The deavage of a C-H bond (bond dissociation requires between 85 and 105 kcal/mol) necessitates a high-energy species, which could quickly become a drawback for the control of chemo-, regio-, and stereoselectivity. Transition metal catalysts are useful reagents for surmounting this problem; they can decrease the kinetic barrier of the reaction yet retain control over selectivity. Transition metal complexes also offer important versatility in having distinct pathways that can lead to activation of the C-H bond. An oxidative addition of the metal in the C-H bond, and a base-assisted metal carbon bond formation in which the base can be coordinated (or not) to the metal complexes are possible. These different C-H bond activation modes provide chemists with several synthetic options. 
In this Account, we discuss recent discoveries involving the versatile NHC-gold(I) and NHC-copper(1) hydroxide complexes (where NHC is N-heterocyclic carbene) showing interesting Bronsted basic properties for C-H bond activation or C-H bond functionalization purposes. The simple and easy synthesis of these two complexes involves their halide-bearing relatives reacting with simple alkali metal hydroxides. These complexes can react cleanly with organic compounds bearing protons with compatible pK(a) values, producing only water as byproduct. It is a very simple protocol indeed and may be sold as a C-H bond activation, although the less flashy "metalation reaction" also accurately describes the process. The synthesis of these complexes has led us to develop new organometallic chemistry and catalysis involving C-H bond activation (metalation) and subsequent C-H bond functionalization. We further highlight applications with these reactions, in areas such as photoluminescence and biological activities of NHC gold(I) and NHC copper(1) complexes.},
  author       = {Gaillard, Sylvain and Cazin, Catherine and Nolan, Steven},
  issn         = {0001-4842},
  journal      = {ACCOUNTS OF CHEMICAL RESEARCH},
  keywords     = {CARBON-HYDROGEN-BONDS,METAL-COMPLEXES,HYDROSILYLATION REACTIONS,ORGANOGOLD COMPOUNDS,CATALYZED REACTIONS,COUPLING REACTIONS,NHC COMPLEXES,FUNCTIONALIZATION,CARBOXYLATION,SILVER},
  language     = {eng},
  number       = {6},
  pages        = {778--787},
  title        = {N-Heterocyclic carbene gold(I) and copper(I) complexes in C-H bond activation},
  url          = {http://dx.doi.org/10.1021/ar200188f},
  volume       = {45},
  year         = {2012},
}

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