Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• cross-coupling of ethers with enamides. Ni(II)-catalyzed CDC of indoles with 1,4-dioxane. Chemo- and regioselective ortho- or para-alkylation of pyridines. Asymmetric CDC of 3,6-dihydro-2H-pyrans with aldehydes. CDC of heterocyclic aromatics with ethers. Indium-catalyzed alkylation of DHPs with 1,3

• esters. Co-catalyzed construction of C(sp2)–C(sp3) bonds. Co-catalyzed CDC of imidazo[1,2-a]pyridines with isochroman. Co-catalyzed C–H alkylation of (benz)oxazoles with ethers. Cobalt-catalyzed CDC between unactivated C(sp2)–H and C(sp3)–H bonds. MnO2-catalyzed CDC of the inactive C(sp3)-H. Oxidative

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• , acrylates, allenes, and alkynes as coupling partners achieving the functionalized C(sp2)–H-olefinated pyridine frameworks via metal catalysis. ortho-C–H Alkenylation In 2012, Huang and co-workers [74] disclosed a ligand-free oxidative cross-coupling reaction of pyridine with acrylates, acrylamides, and

• pyridines with simple alkenes 96, leading to the C3-alkenylated products 97 (Scheme 19). The reaction was based on the previous reports of using of the MPAA ligands in the Pd-catalyzed oxidative cross-coupling reactions discovered by Yu et al. [87]. When 2-methoxypyridine was screened, the reaction resulted

• provides intermediate 161 which upon reductive elimination furnishes the desired product 157 and regeneration of Pd(0) (Scheme 30b). Later in 2014, Kuang and co-workers [101] developed a highly efficient and regioselective oxidative cross-coupling of pyridine N-oxides 9 with five-membered heterocycles 162

New efficient synthesis of polysubstituted 3,4-dihydroquinazolines and 4H-3,1-benzothiazines through a Passerini/Staudinger/aza-Wittig/addition/nucleophilic substitution sequence

• Long Zhao,
• Mao-Lin Yang,
• Min Liu and
• Ming-Wu Ding

Beilstein J. Org. Chem. 2022, 18, 286–292, doi:10.3762/bjoc.18.32

• –Spengler-like cyclization processes [12]. Some 4-substituted 3,4-dihydroquinazolines were prepared by copper-catalyzed oxidative cross coupling of hydroxy intermediates with various nucleophiles [13]. Other 3,4-dihydroquinazolines were also obtained efficiently by intramolecular aza-Wittig reactions [14

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• acids are widely used in stereoselective oxidative/cross-coupling of two aryl counterparts, asymmetric control of aromatic ring formation, atroposelective functionalization of biaryl compounds, and so on [17][29][30]. In this context, Akiyama (2004) described that chiral phosphoric acids (CPAs) have

Copper-promoted/copper-catalyzed trifluoromethylselenolation reactions

• Clément Ghiazza and
• Anis Tlili

Beilstein J. Org. Chem. 2020, 16, 305–316, doi:10.3762/bjoc.16.30

• could be trifluoromethylselenolated that way (Scheme 2) [13][15][16][17]. Mechanistically, the authors postulated the involvement of copper(I)/(III) oxidation states. Oxidative cross-coupling reactions between terminal alkynes using the [(bpy)CuSeCF3]2 complex were also undertaken by the same group to

• already demonstrated its versatility in numerous processes. Nevertheless, its use in oxidative cross-coupling reactions requires stoichiometric amounts of the oxidant, which limits the attractiveness of the method in some cases. Finally, the newly developed electrophilic reagent TsSeCF3 also demonstrated

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• towards chiral 1,4-dicarbonyls bearing tertiary and all-carbon quaternary stereocenters via oxidative cross coupling of 2-acylimidazoles 85 with silyl enol ethers 86 (Scheme 32). Chiral Rh complex 87 was exploited as a Lewis acid catalyst for the purpose of activating the substrate towards anodic

Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones

• Keshaba N. Parida,
• Gulab K. Pathe,
• Shimon Maksymenko and
• Alex M. Szpilman

Beilstein J. Org. Chem. 2018, 14, 992–997, doi:10.3762/bjoc.14.84

• -coupling by using cerium(IV) as a one-electron oxidant [11]. Importantly for the discussion of the present work, Wirth’s strategy relied on a hypervalent iodine [13][14][15] mediated oxidative cross-coupling. Although these processes add a further step to the process, carrying out the cross-coupling in an

Functionalization of N-arylglycine esters: electrocatalytic access to C–C bonds mediated by n-Bu₄NI

• Mi-Hai Luo,
• Yang-Ye Jiang,
• Kun Xu,
• Yong-Guo Liu,
• Bao-Guo Sun and
• Cheng-Chu Zeng

Beilstein J. Org. Chem. 2018, 14, 499–505, doi:10.3762/bjoc.14.35

• ]. Later on, arylation, vinylation and alkynylation of glycine derivatives were also accomplished by the same group (Scheme 1) [13]. Using the Cu(OAc)2/pyrrolidine dual catalysts system, Huang developed the oxidative cross coupling of glycine derivatives with acetone in the presence of TBHP or DDQ as

• terminal oxidants [14]. The protocol was also extended to reactions with 2-alkylquinoline [15] and phenols [16] using O2 and di-tert-butyl peroxide (DTBP) as oxidant, respectively (Scheme 1). A CuCl-catalyzed oxidative cross coupling of glycine derivatives with indoles has been developed by Hou et al

α-Acetoxyarone synthesis via iodine-catalyzed and tert-butyl hydroperoxide-mediateded self-intermolecular oxidative coupling of aryl ketones

• Liquan Tan,
• Cui Chen and
• Weibing Liu

Beilstein J. Org. Chem. 2017, 13, 1079–1084, doi:10.3762/bjoc.13.107

• ketones from aryl ketones using I2 and tert-butyl hydroperoxide (TBHP) [16][17][18] (Scheme 1). Several oxidative cross-coupling methods have been developed for the synthesis of α-acetoxy ketones from ketone derivatives and carboxylic acids [10], benzylic alcohols [19], toluene derivatives [20][21] and

Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

• Tsuyuka Sugiishi,
• Hideki Amii,
• Kohsuke Aikawa and
• Koichi Mikami

Beilstein J. Org. Chem. 2015, 11, 2661–2670, doi:10.3762/bjoc.11.286

• . and Buchwald et al. used the Ruppert–Prakash reagent (CF3–SiMe3) directly as a CF3− source [46][47]. From CF3–SiMe3, Hartwig et al. developed a new combination of Ir-catalyzed C–H borylation and oxidative cross-coupling using [(phen)CF3Cu] [48]. Grushin et al. utilized fluoroform for the preparation

Efficient synthesis of π-conjugated molecules incorporating fluorinated phenylene units through palladium-catalyzed iterative C(sp²)–H bond arylations

• Fatiha Abdelmalek,
• Fazia Derridj,
• Safia Djebbar,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2015, 11, 2012–2020, doi:10.3762/bjoc.11.218

• straightforward and practical method for the synthesis of end-capped pentafluorobenzene-substituted heteroarenes, which are an important class of materials, through palladium-catalyzed oxidative cross-coupling of perfluoroarenes with aromatic heterocycles [36]. Therefore, we decided to investigate the reactivity

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• ; C–H functionalization; C–O bond formation; cross-dehydrogenative coupling; oxidative cross-coupling; Introduction The development of methods for the cross-dehydrogenative coupling (CDC; or oxidative cross coupling) is an important field of modern organic chemistry. These terms commonly refer to

Recent advances in the gold-catalyzed additions to C–C multiple bonds

• He Huang,
• Yu Zhou and
• Hong Liu

Beilstein J. Org. Chem. 2011, 7, 897–936, doi:10.3762/bjoc.7.103

• homogeneous gold-catalyzed oxidative cross-coupling which leads to α-arylenones 190 from propargylic acetates 189 and arylboronic acids has been developed by Zhang’s group (Scheme 35) [86]. This cross-coupling reaction reveals the synthetic potential of Au(I)/Au(III) catalytic cycles. Kimber reported a facile

• conversion of C(sp3)–Au bonds into C(sp3)–C(sp2) bonds is an ongoing challenge. In 2010, Zhang’s group reported the first example in an intermolecular oxidative cross-coupling manner [167]. In their pioneering work, carboamination, carboalkoxylation and carbolactonization of terminal alkenes 341 was achieved

• products were constructed through a formal [2 + 2 + 1] cycloaddition that involved α-carbonyl–carbenoids, nitroso species and external alkenes (Scheme 58). A gold(I)-catalyzed cascade cyclization/oxidative cross-coupling process has been devised to prepare β-alkynyl-γ-butenolides 366 directly from

Au(I)/Au(III)-catalyzed Sonogashira-type reactions of functionalized terminal alkynes with arylboronic acids under mild conditions

• Deyun Qian and
• Junliang Zhang

Beilstein J. Org. Chem. 2011, 7, 808–812, doi:10.3762/bjoc.7.92

• existence of Au(I)/Au(III) catalytic cycles [26][27][28][29][30][31][32]. For instance, Zhang and co-workers have developed a gold-catalyzed oxidative cross-coupling reaction of arylboronic acids with propargyl esters [27], and Selectfluor® – a source of electrophilic fluorine – was used to oxidize the