- α-Bromoacrylic Acids as C1 Insertion Units for Palladium-Catalyzed Decarboxylative Synthesis of Diverse Dibenzofulvenes
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Herein α-bromoacrylic acids have been employed as C1 insertion units to achieve the palladium-catalyzed [4 + 1] annulation of 2-iodobiphenyls, which provides an efficient platform for the construction of diverse dibenzofulvenes. This protocol enables the formation of double C(aryl)-C(vinyl) bonds via a C(vinyl)-Br bond cleavage and decarboxylation. It is particularly noteworthy that the method features a broad substrate scope, and various interesting frameworks, such as bridged ring, fused (hetero)aromatic ring, and divinylbenzene, can be successfully incorporated into the products.
- Zhang, Minghao,Deng, Wenbo,Sun, Mingjie,Zhou, Liwei,Deng, Guobo,Liang, Yun,Yang, Yuan
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supporting information
p. 5744 - 5749
(2021/08/18)
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- NBE-Controlled Palladium-Catalyzed Interannular Selective C-H Silylation: Access to Divergent Silicon-Containing 1,1′-Biaryl-2-Acetamides
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A novel palladium-catalyzed interannular selective C-H silylation of 1,1′-biaryl-2-acetamides is described. The combination of palladium catalyst with copper oxidant enables meta- or ortho-selective C-H silylation by employing hexamethyldisilane as a trimethylsilyl source, which relies on the control of NBE derivatives as a switch, thus providing straightforward access to divergent silicon-containing 1,1′-biaryl-2-acetamides.
- Li, Wenguang,Chen, Wenqi,Zhou, Bang,Xu, Yankun,Deng, Guobo,Liang, Yun,Yang, Yuan
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supporting information
p. 2718 - 2722
(2019/04/16)
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- Metal-Oxidant-Free Cobalt-Catalyzed C(sp2)-H Carbonylation of ortho-Arylanilines: An Approach toward Free (NH)-Phenanthridinones
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A traceless directing group assisted Co-catalyzed C(sp2)-H carbonylation of ortho-arylanilines for the synthesis of free (NH)-phenanthridinones in metal-based-oxidant-free fashion was accomplished. This protocol employs diisopropyl azodicarboxylate as the CO source and oxygen as the sole oxidant, and provides good yields with various functional tolerance. The methodology has been applied for the total synthesis of PARP inhibitor PJ-34. Furthermore, the kinetic isotopic effect experiments reveal the C-H bond cleavage probably occurred in the rate-determining step.
- Ling, Fei,Zhang, Chaowei,Ai, Chongren,Lv, Yaping,Zhong, Weihui
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p. 5698 - 5706
(2018/05/23)
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- AgI-Promoted Difluoromethylation of Isocyanides To Give Difluoromethylated Phenanthridines
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An AgI-mediated ethoxycarbonyldifluoromethylation of isocyanides has been developed. This radical cascade reaction involves the addition of difluoromethylene radical to the isocyanide functionality, and subsequent homolytic aromatic substitution to give difluoromethylated phenanthridines with a good functional-group tolerance.
- Wan, Wen,Xu, Xiaochen,Chen, Yunrong,Jiang, Haizhen,Wang, Yong,Deng, Hongmei,Hao, Jian
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supporting information
p. 3145 - 3151
(2017/06/21)
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- Highly Stereoselective Synthesis of Imine-Containing Dibenzo[b,d]azepines by a Palladium(II)-Catalyzed [5+2] Oxidative Annulation of o-Arylanilines with Alkynes
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A novel palladium(II)-catalyzed [5+2] oxidative annulation of readily available o-arylanilines with alkynes has been developed for building a seven-membered N-heterocyclic architecture containing a biaryl linkage. This method is applicable to a wide range of unprotected o-arylanilines and internal alkynes, and results in the chemoselective preparation of imine-containing dibenzo[b,d]azepines in high yields with excellent diastereoselectivity with respect to the two types of stereogenic elements.
- Zuo, Zhijun,Liu, Jingjing,Nan, Jiang,Fan, Liangxin,Sun, Wei,Wang, Yaoyu,Luan, Xinjun
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supporting information
p. 15385 - 15389
(2016/01/26)
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- Synthesis of 6-(arylthio)phenanthridines by copper-catalyzed tandem reactions of 2-biaryl isothiocyanates with diaryliodonium salts
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A novel copper-catalyzed tandem C-S/C-C bond-forming reaction of 2-biaryl isothiocyanates with diaryliodonium salts was developed. This is the first general approach to synthesize phenanthridines from 2-biaryl isothiocyanates. This methodology has been successfully applied to the synthesis of trisphaeridine.
- Guo, Weisi,Li, Shoulei,Tang, Lin,Li, Ming,Wen, Lirong,Chen, Chao
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supporting information
p. 1232 - 1235
(2015/03/14)
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- Direct synthesis of N -H carbazoles via iridium(III)-catalyzed intramolecular C-H amination
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The iridium-catalyzed dehydrogenative cyclization of 2-aminobiphenyls proceeds smoothly in the presence of a copper cocatalyst under air as a terminal oxidant through intramolecular direct C-H amination to produce N-H carbazoles. A similar iridium/copper system can also catalyze the unprecedented dimerization reaction of 2-aminobiphenyl involving 2-fold C-H/N-H couplings.
- Suzuki, Chiharu,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information
p. 1597 - 1600
(2015/03/30)
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- Photoredox-Catalyzed Tandem Insertion/Cyclization Reactions of Difluoromethyl and 1,1-Difluoroalkyl Radicals with Biphenyl Isocyanides
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Using visible-light photoredox conditions, difluoromethylation and 1,1-difluoroalkylation of biphenyl isocyanides have allowed the synthesis of a series of 6-(difluoromethyl)- and 6-(1,1-difluoroalkyl)phenanthridines via tandem addition/cyclization/oxidation processes. The reactions are carried out in wet dioxane at room temperature using fac-Ir(ppy)3 as catalyst to form a large variety of substituted phenanthridine products in good to excellent yield.
- Zhang, Zuxiao,Tang, Xiaojun,Dolbier, William R.
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supporting information
p. 4401 - 4403
(2015/09/28)
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- Visible-light-promoted radical C-H trifluoromethylation of free anilines
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The trifluoromethyl-substituted anilines are biologically active compounds and useful building blocks. In this communication, we have developed the first visible-light-induced radical trifluoromethylation of free anilines with the commercially available and easily handled Togni reagent at room temperature. The resulting products were successfully transformed into a variety of valuable fluorine-containing molecules and heterocyclic compounds. This protocol provides an economical and powerful route to trifluoromethylated free anilines.
- Xie, Jin,Yuan, Xiangai,Abdukader, Ablimit,Zhu, Chengjian,Ma, Jing
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supporting information
p. 1768 - 1771
(2014/04/17)
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- Ruthenium-catalyzed regioselective C-H alkenylation directed by a free amino group
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The ruthenium-catalyzed alkenylation reactions of 2-aminobiphenyls and cumylamine proceed smoothly to produce the corresponding regioselectively alkenylated products. These reactions involve a C-H bond cleavage directed by their free amino groups.
- Suzuki, Chiharu,Hirano, Koji,Satoh, Tetsuya,Miura, Masahiro
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supporting information
p. 3990 - 3993
(2013/09/02)
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- PhI(OAc)2-mediated synthesis of 6-(trifluoromethyl) phenanthridines by oxidative cyclization of 2-isocyanobiphenyls with CF 3SiMe3 under metal-free conditions
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A mild and efficient method for the synthesis of 6-(trifluoromethyl) phenanthridines through oxidative cyclization of 2-isocyanobiphenyls with CF3SiMe3 under metal-free conditions was developed. The reaction allows the direct formation of C-CF3 bonds and rapid access to phenanthridine ring systems in one catalytic cycle.
- Wang, Qile,Dong, Xichang,Xiao, Tiebo,Zhou, Lei
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supporting information
p. 4846 - 4849
(2013/10/08)
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- Direct intermolecular aniline ortho- arylation via benzyne intermediates
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A method for direct, transition-metal-free ortho-arylation of anilines by aryl chlorides, bromides, fluorides, and triflates has been developed. This methodology provides the most direct approach to 2-arylanilines since no protecting or directing groups on nitrogen are required. The arylation is functional-group tolerant, with alkene, ether, trifluoromethyl, dimethylamino, carbonyl, chloro, and cyano functionalities tolerated. Phenylation of enantiopure binaphthyldiamine affords a product with >99% ee.
- Truong, Thanh,Daugulis, Olafs
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supporting information
p. 5964 - 5967
(2013/02/22)
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- Transition-metal-free direct arylation of anilines
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Aryne arylation: A new method of direct arylation is reported for aniline substrates. The reaction uses benzyne to synthesize a variety of aminobiaryls under mild conditions (see scheme), requiring no stoichiometric metalation or transition-metal catalysis. An ene mechanism is implicated, and conveys excellent functional group tolerance relative to metal-mediated processes. Copyright
- Pirali, Tracey,Zhang, Fengzhi,Miller, Anna H.,Head, Jenna L.,McAusland, Donald,Greaney, Michael F.
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p. 1006 - 1009
(2012/02/16)
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- A novel catalytic process for trifluoromethylation of bromoaromatic compounds
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The palladium-catalyzed trifluoromethylation of aryl bromides has been achieved in micellar media. The micellar conditions result in enhanced yields and are applicable to bromoaromatics with ketone, aldehyde, hydroxyl and amine functionalities.
- Samant, Bhupesh S.,Kabalka, George W.
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supporting information; experimental part
p. 7236 - 7238
(2011/08/22)
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- Pd-catalyzed sequential C-C and C-N bond formations for the synthesis of N-heterocycles: Exploiting protecting group-directed C-H activation under modified reaction conditions
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Easy & efficient: A Pd-catalyzed domino olefination/conjugate addition reaction of N-Ts-2-arylanilines with activated olefins has been achieved at ambient temperature under the newly defined reaction conditions. This process highlighted the directing effect of the N-protecting group in C-H activation, displayed broad substrate scope with wide functional group compatibility; thus rendering a straightforward entry to a wide variety of N-heterocycles such as dihydrophenanthridines.
- Kim, Byung Seok,Lee, Sun Young,Youn, So Won
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supporting information; experimental part
p. 1952 - 1957
(2011/11/04)
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- Rh2(II)-catalyzed synthesis of carbazoles from biaryl azides
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An array of carbazoles (23 examples) can be synthesized from substituted biaryl azides at 60 °C using substoichio-metric quantities of Rh 2(O2CC3F7)4 or Rh 2(O2CC7H15)4.
- Stokes, Benjamin J.,Jovanovic, Brankica,Dong, Huijun,Richert, Kathleen J.,Riell, Ryan D.,Driver, Tom G.
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supporting information; experimental part
p. 3225 - 3228
(2009/08/07)
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- Thermal Diels-Alder reactions of 3-(benzoylamino)-6-(polyfluoroalkyl)pyran- 2-ones - New synthesis of p-(polyfluoroalkyl)anilines
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A new practical method for the regioselective synthesis of the N-benzoyl-4-(polyfluoroalkyl) anilines 5a-g by thermal Diels-Alder cycloaddition of 5-substituted 3-(benzoylamino)-6-(polyfluoroalkyl)pyran-2-ones 1a-e with fluorostyrenes 2 and 7, acetylenes
- Tolmachova, Nataliya A.,Gerus, Igor I.,Vdovenko, Sergey I.,Essers, Michael,Froehlich, Roland,Haufe, Guenter
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p. 4704 - 4709
(2007/10/03)
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