Recent Developments in Catalytic Aryl Coupling Reactions

Catellani, Marta; Motti, Elena; Cà, Nicola Della; Ferraccioli, Raffaella

doi:10.1002/ejoc.200700312

Cited by 78 publications

(22 citation statements)

References 128 publications

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“…23 This collection of recent reports follows on from the excellent comprehensive review by Alberico et al 13 which did not cover much of 2006 and any of 2007/2008 and also excludes aryl-aryl bond formation via oxidative coupling. 24,25 We herein review the literature up to October 2008 on the evolution of direct arylation.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in aryl–aryl bond formation by direct arylation

2009

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The abundance of the biaryl structural motif in natural products, in biologically active molecules and in materials chemistry has positioned aryl-aryl (Ar-Ar) bond formation high on the agenda of synthetic chemists. For decades well-known reactions such as the Mizoroki-Heck and Suzuki-Miyaura have been the methods of choice to furnish biaryls. More recently, however, alternative methods, most notably direct arylation via C-H activation, have become the focus of many research groups. Compared to traditional methods, direct arylation affords Ar-Ar compounds in fewer steps by removing the need for prefunctionalisation. Furthermore, given that either one or two hydrogens are targeted, less waste and good atom economy are features of this methodology. This critical review covers, in the main part, reports from January 1, 2006, to October 22, 2008 (117 references).

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Section: Introductionmentioning

confidence: 99%

Recent advances in aryl–aryl bond formation by direct arylation

2009

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“…Recently, direct arylation of arenes via C-H bond activation has received significant attention and the corresponding mechanism mainly involved C-H insertion as the key step. [16][17][18][19][20][21][22][23][24][25][26]27 The noble transition metals, such as, Pd, Rh, Ru, and Ir catalyzed direct arylation of arenes, typically called directing-group-containing arenes, can be regarded in one category. 22-24,28-31 Sets of heterocycles were directly arylated successfully in many examples and could be regarded in one category.…”

Section: His Research Focuses On Transition Metal-catalyzed C-h Activ...mentioning

confidence: 99%

Arylation of unactivated arenes

et al. 2010

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“…Geometrical features of these species are summarized, as follows: First, HBzq approaches the Pd complex to form PC 1 . In PC 1 , the C 9 -C 10 methods, respectively. 52 The MP4(SDQ)-calculated ΔE and ΔG 0 values are considerably negative, as shown in Fig.…”

Section: The C-h Activation Of Hbzqmentioning

confidence: 99%

“…In organometallic chemistry, the C-C bond formation reaction catalyzed by transition metal complex is one of the most important research subjects. [1][2][3][4][5][6][7][8][9][10][11][12] The metal-catalyzed cross-coupling reaction is widely employed for the C-C bond formation such as the Stille coupling reaction 13 and the Suzuki-Miyaura coupling reaction. 14 High selectivity, 15 functional group tolerance, and use of the mild reaction conditions make these processes sensible choice for the C-C bond formation even in the complicated synthesis of natural product.…”

Section: Introductionmentioning

confidence: 99%

Pd(ii)-promoted direct cross-coupling reaction of arenes via highly regioselective aromatic C–H activation: a theoretical study

et al. 2010

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The direct cross-coupling reaction of arenes promoted by Pd(OAc)(2) is synthetically very useful because the preparation of a haloarene as a substrate is not necessary. This reaction interestingly only occurs in the presence of benzoquinone (BQ). DFT, MP2 to MP4(SDQ), and CCSD(T) computations elucidated the whole mechanism of this cross-coupling reaction and the key roles of BQ. The first step is the heterolytic C-H activation of benzo[h]quinoline (HBzq) by Pd(OAc)(2) to afford Pd(Bzq)(OAc). The Pd center is more electron-rich in Pd(Bzq)(OAc) than in Pd(OAc)(2). Hence, BQ easily coordinates to Pd(Bzq)(OAc) with a low activation barrier to afford a distorted square planar complex Pd(Bzq)(OAc)(BQ) which is as stable as Pd(Bzq)(OAc). Then, the second C-H activation of benzene occurs with a moderate activation barrier and small endothermicity. The final step is the reductive elimination which occurs with little barrier. The rate-determining step of the overall reaction is the second C-H activation whose activation barrier is considerably higher than that of the first C-H activation. BQ plays a key role in accelerating this reaction; (i) the phenyl group must change its position a lot to reach the transition state in the reductive elimination from the square planar intermediate Pd(Ph)(Bzq)(OAc) but only moderately in the reaction from the trigonal bipyramidal intermediate Pd(Ph)(Bzq)(OAc)(BQ). This is because BQ suppresses the phenyl group to take a position at a distance from the Bzq. (ii) BQ stabilizes the transition state and the product complex by the back-donation interaction. In the absence of BQ, the reductive elimination step has a much higher activation barrier. Though it was expected that the BQ coordination accelerates the second C-H activation of benzene by decreasing the electron density of Pd in Pd(Bzq)(OAc), the activation barrier of this second C-H activation is little influenced by BQ.

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Recent Developments in Catalytic Aryl Coupling Reactions

Cited by 78 publications

References 128 publications

Recent advances in aryl–aryl bond formation by direct arylation

Recent advances in aryl–aryl bond formation by direct arylation

Arylation of unactivated arenes

Pd(ii)-promoted direct cross-coupling reaction of arenes via highly regioselective aromatic C–H activation: a theoretical study

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