Functionalization of Primary Carbon−Hydrogen Bonds of Alkanes by Carbene Insertion with a Silver-Based Catalyst

Urbano, Juan; Belderraín, Tomás R.; Nicasio, M. Carmen; Trofimenko, Swiatoslaw; Díaz‐Requejo, M. Mar; Pérez, Pedro J.

doi:10.1021/om050024k

Cited by 103 publications

(77 citation statements)

References 27 publications

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“…The metal carbenoids behave as very electrophilic species and the electron-withdrawing ester group reinforces the high reactivity, generating a system characterized by poor regioselectivity between different C-H bonds [27][28][29] . In recent years, extensive efforts have been made to attenuate the carbenoid reactivity by altering the nature of the catalysts, with some improvements having been made by using very bulky ligands with copper 30 and silver 31 complexes. The major breakthrough in this field, however, was the discovery that carbenoids functionalized with both donor and acceptor groups were much more chemoselective than the traditional carbenoids, as shown in Fig.…”

Section: C-h Functionalization By Metal Carbenoidsmentioning

confidence: 99%

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Davies

Manning

2008

Nature

2,145

812

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Novel reactions that can selectively functionalize carbon-hydrogen bonds are of intense interest to the chemical community because they offer new strategic approaches for synthesis. A very promising 'carbon-hydrogen functionalization' method involves the insertion of metal carbenes and nitrenes into C-H bonds. This area has experienced considerable growth in the past decade, particularly in the area of enantioselective intermolecular reactions. Here we discuss several facets of these kinds of C-H functionalization reactions and provide a perspective on how this methodology has affected the synthesis of complex natural products and potential pharmaceutical agents.I n 2006, 31 new chemical entities were introduced to the world pharmaceutical market and 2,075 molecules were in phase I or II of clinical development 1 . The majority of these were smallmolecule (relative molecular mass ,1,000) organic compounds 2 . As knowledge about the specific interactions of drugs in vivo increases, often so does the structural complexity of new drug targets. A major obstacle to the development of such drugs is the difficulty associated with synthesizing large quantities in an economical fashion, because complex multi-step syntheses are usually required. In the general media, it is often overlooked that the accessibility of the components required for these new treatments will often govern their eventual success or failure. Likewise, a design element of any pharmaceutical agent is the expectation that the target compounds can be made economically. Therefore, new strategies for synthesis can become enabling technologies, making available new targets and materials that would have been previously out of range. For example, new methodologies such as metal-catalysed crosscoupling 3 and olefin metathesis 4-6 have rapidly become central transformations in the synthesis of new pharmaceutical agents. Selective C-H functionalization is a class of reactions that could lead to a paradigm shift in organic synthesis, relying on selective modification of ubiquitous C-H bonds of organic compounds instead of the standard approach of conducting transformations on pre-existing functional groups. The reactive sites in each type of transformation are very different, as illustrated in Fig. 1.The many opportunities associated with C-H functionalization has made this field an active area of research. Organometallic chemists have focused much attention on developing 'C-H activation' strategies, whereby a highly reactive metal complex inserts into a C-H bond, activating the system for subsequent transformations 7-9 . One of the major challenges associated with this chemistry has been to render it catalytic in the metal complex 10 . A partial solution to this problem has been to use neighbouring functionality to direct less reactive metal complexes to the site for functionalization. Numerous reviews have been written about this method for C-H functionalization [11][12][13][14][15][16][17] . Here, however, we highlight another approach, in which a divalent c...

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Section: C-h Functionalization By Metal Carbenoidsmentioning

confidence: 99%

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Davies

Manning

2008

Nature

2,145

812

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“…In 2005, Pérez and coworkers developed a highly active silver catalyst [Tp Br3 Ag] 2 (Me 2 CO) 2 for the transformation of sp 3 C-H bond of alkanes with carbene species (Scheme 3) [20]. Compared to silver catalyst 1, the substitution of ligand in silver catalysts 2 was changed from CF 3 (catalyst 1) to Br (catalyst 2) and showed higher efficiency of carbene insertion into sp 3 C-H bonds of various alkanes with EDA.…”

Section: Direct C-c Bond Formationmentioning

confidence: 99%

Silver-Mediated Direct sp3 C–H Bond Functionalization

Zhou

Shi

2015

Topics in Organometallic Chemistry

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Direct sp 3 C-H bond functionalization is an efficient, straightforward, and powerful method to construct new C-X (X¼C, N, F, S) bonds from nonfunctionalized aliphatic motif of organic molecules, which has been used in late-stage modification of complex molecules. In this chapter, the recent developments of silver-mediated direct sp 3 C-H functionalizations are reviewed, categorized by C-C bond formation (C-H insertion), C-N bond formation (intramolecular and intermolecular amination/amidation), C-F bond formation, and C-S bond formation.

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“…8.3), although no chemical yields were reported in either case. 20 The corresponding Cu-scorpionate complexes function well as cyclopropanation catalysts. 19,[21][22][23] Davies and Thompson have demonstrated that several donor-acceptor diazo compounds (35 and 37) participate in selective silver-catalyzed cyclopropanation of a variety of olefins with AgSbF 6 as catalyst at reflux in CH 2 Cl 2 (Schemes 8.6 and 8.7).…”

Section: Cyclopropanationmentioning

confidence: 99%

Silver Carbenoids

Lovely¹

2010

Silver in Organic Chemistry

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Functionalization of Primary Carbon−Hydrogen Bonds of Alkanes by Carbene Insertion with a Silver-Based Catalyst

Cited by 103 publications

References 27 publications

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Catalytic C–H functionalization by metal carbenoid and nitrenoid insertion

Silver-Mediated Direct sp3 C–H Bond Functionalization

Silver Carbenoids

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