Transition metal-catalyzed arylation of unactivated C(sp3)–H bonds

Baudoin, Olivier

doi:10.1039/c1cs15058h

Cited by 786 publications

(174 citation statements)

References 91 publications

(67 reference statements)

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“…Furthermore, the primary amines with a cyclic alkyl group reacted smoothly in this catalytic system (2j and 2k). Although many successful examples for functionalizing unactivated secondary sp 3 C−H bonds have been reported with the installation of a mono-or bidentate directing group on the substrates [5][6][7][8][9][10][11][12][13][14][15] , direct functionalization of these bonds remains a great challenge with carbonyl compounds using a transient directing group 37 and free aliphatic amines 23,30,31 , presumably due to the inherent steric hindrance. In this catalytic system, substrate 1l with cyclic methylene C−H bonds provided the γ-arylated product 2l in 23% yield, while arylation of noncyclic secondary C−H bonds was not realized.…”

Section: Resultsmentioning

confidence: 99%

Site-selective C–H arylation of primary aliphatic amines enabled by a catalytic transient directing group

2016

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Abstract. Transition metal-catalyzed direct C−H bond functionalization of aliphatic amines is of great importance in organic and medicinal chemistry research. While several methods have been developed for the direct sp 3 C−H functionalization of secondary and tertiary aliphatic amines, site-selective functionalization of primary aliphatic amines remains a challenge. Here we report the direct highly siteselective arylation of primary alkylamines via a palladium-catalyzed C−H bond functionalization process on unactivated sp 3 carbons with catalytic glyoxylic acid as a novel, inexpensive, and transient directing group. With this approach, a wide array of γ-arylated primary alkylamines, important structural motifs in organic and medicinal chemistry, were prepared without any protection or deprotection steps.Aliphatic amines are ubiquitously present in pharmaceuticals with a wide range of biological activities 1,2 .

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Section: Resultsmentioning

confidence: 99%

Site-selective C–H arylation of primary aliphatic amines enabled by a catalytic transient directing group

2016

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“…Palladium and copper salts have been utilized for these kinds of transformations. Due to certain flaws of metal-catalysed reactions, researchers have moved towards transition metal-free cross-coupling reactions which belong to the most recently emerging transformations in recent organic synthesis [12]. These X-arylations by TMF reactions can be carried out in the presence of various bases, organo-catalysts and various energy sources.…”

Section: Introductionmentioning

confidence: 99%

Synthetic journey towards transition metal-free arylations

Roopan

Palaniraja

2014

Res Chem Intermed

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In general, aryl-aryl transformations were investigated via transition metal-catalysed reactions. However, transition metal-mediated organic synthesis provided higher yields but has some flaws such as high cost, and the need for careful exclusion of air and moisture during the reactions. Possibly, there may be contamination of the product from traces of heavy metals present. To overcome these kinds of disadvantages, continuous efforts have been focused on the recent development of aryl-aryl formation through transition metal-free (TMF) reactions. However, most of these cross-couplings reaction were limited to hetero and electron-rich arenes which require strong inorganic bases. Our critical review includes a synthetic pathway to prepared X-aryl (X = C, N, O and S) motif by a transition metal-free scenario. Formerly, TMF reactions were carried out by various sources like strong bases, diazodium salt, aryliodonium salt, organo-catalysts and versatile energy sources like microwave heating, visible light and photochemical reactor. In this review, we have focused on the transition metal-free arylations.

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“…[2][3][4] Recently,atransition-metal-catalyzed functionalization of CÀH bonds has been significantly developedf or the synthesis of varioush eterocyclic frameworks from simple substrates. [5] Heck et al demonstrated that cyclopalladated benzaldimines tetrafluoroborates, which were formed from aryl aldimines and AgBF 4 by CÀHa ctivation, reactedwith alkynes to produce isoquinoline salts in yields up to 80 %, but the metal-catalyzed CÀHa ctivation was not the key step.…”

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confidence: 98%