Copper-catalyzed trifluoromethylation of alkenes with an electrophilic trifluoromethylating reagent

• Xiao-Ping Wang,
• Jin-Hong Lin,
• Cheng-Pan Zhang,
• Ji-Chang Xiao and
• Xing Zheng

Beilstein J. Org. Chem. 2013, 9, 2635–2640, doi:10.3762/bjoc.9.299

• , reaction 3). Transition metal-catalyzed trifluoromethylation of terminal alkenes has been reported by several groups. However, these methods focused on the formation of Csp3–CF3 bonds [46][47][48][49][50][51][52][53][54][55][56]. In copper-catalyzed reactions with electrophilic trifluoromethylating

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• , 69263 Lyon, Cedex 09, France 10.3762/bjoc.9.287 Abstract In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond

• formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp

• trifluoromethylation reactions [22][23][24][25][26][27][28]. The present review focuses on fundamental achievements in the field of transition metal-catalyzed mono-, di- and trifluoromethylation as well as trifluoromethylthiolation of sp² carbon atoms. We present the different developments according to the reaction

Triol-promoted activation of C–F bonds: Amination of benzylic fluorides under highly concentrated conditions mediated by 1,1,1-tris(hydroxymethyl)propane

• Pier Alexandre Champagne,
• Alexandre Saint-Martin,
• Mélina Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2013, 9, 2451–2456, doi:10.3762/bjoc.9.283

• number of transition metal-catalyzed methods [1][2][3][4][5][6][7][8][9] and transition-metal-free methodologies [1][10][11][12] have been developed. In continuation with our interest in the activation of C–F bonds [13][14][15][16], we have recently reported that it was possible to enable the use of

Synthetic scope and DFT analysis of the chiral binap–gold(I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

• María Martín-Rodríguez,
• Luis M. Castelló,
• Carmen Nájera,
• José M. Sansano,
• Olatz Larrañaga,
• Abel de Cózar and
• Fernando P. Cossío

Beilstein J. Org. Chem. 2013, 9, 2422–2433, doi:10.3762/bjoc.9.280

• enantioselective and/or diastereoselective processes have been focussed on the elaboration of enantiomerically enriched new non-proteinogenic α-amino acids, such as Michael-type additions [6][7], transition metal-catalyzed allylations [8], Mannich-type additions [9], aldol-type reactions [10], and for other

An easy direct arylation of 5-pyrazolones

• Hao Gong,
• Yiwen Yang,
• Zechao Wang and
• Chunxiang Kuang

Beilstein J. Org. Chem. 2013, 9, 2033–2039, doi:10.3762/bjoc.9.240

• synthesize a new series of heterocyclic compounds containing the pyrazolone moiety. The reaction of pyrazolones with arylboronic acids is an attractive approach for the synthesis of arylpyrazolone [15][16]. However, it often needs pre-formation of halo-pyrazolones. Transition metal-catalyzed direct arylation

Gold(I)-catalyzed formation of furans from γ-acyloxyalkynyl ketones

• Marie Hoffmann,
• Solène Miaskiewicz,
• Jean-Marc Weibel,
• Patrick Pale and
• Aurélien Blanc

Beilstein J. Org. Chem. 2013, 9, 1774–1780, doi:10.3762/bjoc.9.206

• construct the furan motif [4][5]. Among them, late transition metal-catalyzed intra- or intermolecular cyclizations of oxygenated functionalities on unsaturated carbon–carbon bonds proved to be powerful synthetic methods due to their mildness, efficiency and diversity [6][7]. In the last decade, gold

Iron-catalyzed decarboxylative alkenylation of cycloalkanes with arylvinyl carboxylic acids via a radical process

• Jincan Zhao,
• Hong Fang,
• Jianlin Han and
• Yi Pan

Beilstein J. Org. Chem. 2013, 9, 1718–1723, doi:10.3762/bjoc.9.197

• , numerous transition-metal-catalyzed processes, such as Pd [12][13][14][15][16][17][18], Cu [19][20][21][22][23], Ru [24][25][26][27], Rh [28][29][30][31], Co [32][33][34], Au [35][36], Ir [37][38][39], Fe [40][41][42][43] and other metals [44][45][46][47], have been developed for sp3 C–H activation

Aerobic radical multifunctionalization of alkenes using tert-butyl nitrite and water

• Daisuke Hirose and
• Tsuyoshi Taniguchi

Beilstein J. Org. Chem. 2013, 9, 1713–1717, doi:10.3762/bjoc.9.196

• precursor of a 5-amino-1,4-diol, and the access from simple aliphatic alkenes in one step is unprecedented. The functionalization of unreactive sp3 C–H bonds using a radical 1,5-hydrogen shift is an old methodology compared with modern transition metal-catalyzed C–H activation reactions [25][26][27], but

Organocatalyzed enantioselective desymmetrization of aziridines and epoxides

• Ping-An Wang

Beilstein J. Org. Chem. 2013, 9, 1677–1695, doi:10.3762/bjoc.9.192

• based on transition-metal catalyzed reactions has given rise to a variety of significant achievements both in academic and industrial chemistry [2][3]. Desymmetrization is the modification of a molecule which results in the loss of symmetry elements such as a mirror plane, a center of inversion or a

A Lewis acid-promoted Pinner reaction

• Dominik Pfaff,
• Gregor Nemecek and
• Joachim Podlech

Beilstein J. Org. Chem. 2013, 9, 1572–1577, doi:10.3762/bjoc.9.179

• reaction with a 4 N hydrogen chloride solution in cyclopentyl methyl ether (CPME) [7]. An ionic liquid based on a sulfonic acid was used by Jiang et al. [8], where this method has only been applied to aliphatic nitriles. A transition metal-catalyzed Pinner reaction using dihydridotetrakis

A³-Coupling catalyzed by robust Au nanoparticles covalently bonded to HS-functionalized cellulose nanocrystalline films

• Jian-Lin Huang,
• Derek G. Gray and
• Chao-Jun Li

Beilstein J. Org. Chem. 2013, 9, 1388–1396, doi:10.3762/bjoc.9.155

• environmental pollution [1][2]. In the past few decades, aqueous-phase organic reactions have achieved great success [3][4][5]. The classic examples include the Grignard-type reactions [6][7], transition-metal catalyzed C–C bond formations [8][9] and cross-dehydrogenative coupling (CDC) reactions [10][11][12

Photoinduced synthesis of unsymmetrical diaryl selenides from triarylbismuthines and diaryl diselenides

• Yohsuke Kobiki,
• Shin-ichi Kawaguchi,
• Takashi Ohe and
• Akiya Ogawa

Beilstein J. Org. Chem. 2013, 9, 1141–1147, doi:10.3762/bjoc.9.127

• catalysts is desirable. On the other hand, triarylbismuthines are gaining interest as useful arylation reagents, because organobismuth compounds are nontoxic and have excellent reactivity, which has led to several applications in organic synthesis [33]. Therefore, numerous transition-metal-catalyzed

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

• Kei Murakami and
• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34

• involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1) alkynes bearing an electron-withdrawing

• could be employed for uncatalyzed intermolecular carbometalation. Naturally, many groups envisioned transition-metal-catalyzed carbometalation reactions that directly convert alkynes and alkenes to new organomagnesium and organozinc reagents [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28

• zirconium salt, the examples of transition-metal-catalyzed carbometalation of dialkylacetylenes were limited only to carboboration [109][110] and carbostannylation [111]. In 2005, Shirakawa and Hayashi reported iron/copper-cocatalyzed arylmagnesiation of dialkylacetylenes [112]. This is the first successful

Palladium-catalyzed C–N and C–O bond formation of N-substituted 4-bromo-7-azaindoles with amides, amines, amino acid esters and phenols

• Rajendra Surasani,
• Dipak Kalita,
• A. V. Dhanunjaya Rao and
• K. B. Chandrasekhar

Beilstein J. Org. Chem. 2012, 8, 2004–2018, doi:10.3762/bjoc.8.227

• -research chemists. Therefore, transition metal-catalyzed coupling of amino acids and its derivatives finds popularity in various coupling protocols [58]. A copper(I) iodide catalyzed coupling reaction of haloindoles with α-amino acids was reported by Ishikawa et al. [59]. Indole and azaindole moieties

Rh(III)-catalyzed directed C–H bond amidation of ferrocenes with isocyanates

• Satoshi Takebayashi,
• Tsubasa Shizuno,
• Takashi Otani and
• Takanori Shibata

Beilstein J. Org. Chem. 2012, 8, 1844–1848, doi:10.3762/bjoc.8.212

• economy, and requires stoichiometric amounts of metal reagents. Functionalization of ferrocene derivatives by transition-metal-catalyzed enantioselective C–H activation is a potentially more atom-economical alternative. However, only a few catalytic C–H activation reactions of ferrocenes have been

Copper-catalyzed CuAAC/intramolecular C–H arylation sequence: Synthesis of annulated 1,2,3-triazoles

• Rajkumar Jeyachandran,
• Harish Kumar Potukuchi and
• Lutz Ackermann

Beilstein J. Org. Chem. 2012, 8, 1771–1777, doi:10.3762/bjoc.8.202

• ; heteroarenes; triazoles; Introduction Transition-metal-catalyzed C–H bond functionalizations are increasingly viable tools for step-economical syntheses of various valuable bioactive compounds [1][2][3], which avoid the preparation and use of preactivated substrates [4][5][6][7][8][9][10][11][12][13][14][15

Iridium-catalyzed intramolecular [4 + 2] cycloadditions of alkynyl halides

• Andrew Tigchelaar and
• William Tam

Beilstein J. Org. Chem. 2012, 8, 1765–1770, doi:10.3762/bjoc.8.201

• alkynes, [2 + 2 + 2] cyclotrimerizations of alkynes [14][15], and Pauson–Khand-type [2 + 2 + 1] cycloadditions of enynes [17][18][19] and allenynes [20]; however, Ir-catalyzed [4 + 2] cycloadditions are rare in the literature [26][27]. Transition-metal-catalyzed (TMC) [4 + 2] cycloadditions are an

• examples of intramolecular TMC [4 + 2] cycloadditions of diene-tethered alkynes. Reaction pathways of alkynyl halides in transition-metal-catalyzed reactions. Synthesis of diene-tethered alkynyl halides 1c and 1e. Synthesis of diene-tethered alkynyl halide 1g. Unsuccessful cycloaddition attempts with

C2-Alkylation of N-pyrimidylindole with vinylsilane via cobalt-catalyzed C–H bond activation

• Zhenhua Ding and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2012, 8, 1536–1542, doi:10.3762/bjoc.8.174

• efficient and regioselective functionalization of indole derivatives [4][5][6]. Over the past decade, transition-metal-catalyzed direct functionalization has emerged as a powerful strategy for the direct introduction of aryl and alkenyl groups to the C2 and C3 positions of indole [7][8][9]. The situation is

• C2-lithiation with a stoichiometric lithium base or indol-2-yl radicals generated from 2-halogenated indoles [12][13][14][15][16][17]. Examples of direct C2-alkylation via transition-metal-catalyzed C–H activation are still limited [18][19][20], while Jiao and Bach recently reported an elegant

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

• Marcus Frings,
• Isabelle Thomé and
• Carsten Bolm

Beilstein J. Org. Chem. 2012, 8, 1443–1451, doi:10.3762/bjoc.8.164

• diastereoselective transformations or as chiral ligands in enantioselective metal catalysis [25][26][27][28][29][30][31][32][33]. With respect to the latter field we have recently demonstrated that various ligands bearing a sulfonimidoyl moiety lead to excellent stereoselectivities in transition metal-catalyzed

Organocatalytic C–H activation reactions

• Subhas Chandra Pan

Beilstein J. Org. Chem. 2012, 8, 1374–1384, doi:10.3762/bjoc.8.159

• enantioselectivity for their reaction [25]. Organocatalytic sp2 C–H bond activation reactions The catalytic cross-coupling of arenes and aryl halides to construct biaryl compounds is an important area in synthetic organic chemistry. Transition-metal-catalyzed biaryl synthesis from unactivated arenes by C–H

Palladium-catalyzed substitution of (coumarinyl)methyl acetates with C-, N-, and S-nucleophiles

• Kalicharan Chattopadhyay,
• Erik Fenster,
• Alexander J. Grenning and
• Jon A. Tunge

Beilstein J. Org. Chem. 2012, 8, 1200–1207, doi:10.3762/bjoc.8.133

• ]. Due to the ambiphilic nature of the heterocyclic ring of coumarin, this core-structure undergoes a diverse array of coupling reactions, such as halogenations [25], cycloadditions [26][27][28][29][30][31][32], conjugate additions [33][34][35][36][37] and transition-metal-catalyzed C–H activation

Sonogashira–Hagihara reactions of halogenated glycals

• Dennis C. Koester and
• Daniel B. Werz

Beilstein J. Org. Chem. 2012, 8, 675–682, doi:10.3762/bjoc.8.75

• preparations of alkyl- and aryl-C-glycosides rely on glycals as starting materials. Transition-metal-catalyzed cross-coupling reactions play a key role in the assembly of these structures; thus, many metalated glycals have been employed in their synthesis. Scheme 1 provides a brief overview. In 1990 Beau and

Organic synthesis using (diacetoxyiodo)benzene (DIB): Unexpected and novel oxidation of 3-oxo-butanamides to 2,2-dihalo-N-phenylacetamides

• Wei-Bing Liu,
• Cui Chen,
• Qing Zhang and
• Zhi-Bo Zhu

Beilstein J. Org. Chem. 2012, 8, 344–348, doi:10.3762/bjoc.8.38

• , easy handling, clean transformation, and reactivity, which is similar to heavy-metal-based oxidants, including harmful elements, such as Pb(IV), Hg(II), and Tl(III), as well as transition metal-catalyzed processes [24][25][26][27][28][29][30]. Recently, we reported an efficient acetoxylation approach

Recent advances in direct C–H arylation: Methodology, selectivity and mechanism in oxazole series

• Cécile Verrier,
• Pierrik Lassalas,
• Laure Théveau,
• Guy Quéguiner,
• François Trécourt,
• Francis Marsais and
• Christophe Hoarau

Beilstein J. Org. Chem. 2011, 7, 1584–1601, doi:10.3762/bjoc.7.187

• , aminomethylation, sulfuration, oxygenation). However, aryllithiums can rarely be directly involved in transition-metal-catalyzed cross-coupling reactions and are usually transformed into organometallic fragments suitable for efficient Negishi, Stille, Suzuki–Miyaura, and Hiyama cross-coupling reactions [1][2

• electrophilic reactions as well as transition-metal-catalyzed cross-coupling reactions. By contrast, the methodology for transition-metal-catalyzed direct arylation [13][14][15][16][17][18] is based upon the use of various catalytic metalation processes, such as electrophilic metalation, oxidative addition

• ) catalysis with arylbromides (Scheme 30) [80][81]. Transition metal-catalyzed dehydrogenative cross-coupling Last year, Hu and You reported the first extended study of Pd(II)- and Cu(II)- catalyzed oxidative C–H/C–H cross-coupling of electron-rich heteroarenes, including benzoxazole coupled with 2

Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes

• Elena Borsini,
• Gianluigi Broggini,
• Andrea Fasana,
• Chiara Baldassarri,
• Angelo M. Manzo and
• Alcide D. Perboni

Beilstein J. Org. Chem. 2011, 7, 1468–1474, doi:10.3762/bjoc.7.170

• -azepines. Keywords: C–C coupling; gold catalysis; homogeneous catalysis; nitrogen heterocycles; rearrangement; Introduction Intramolecular transition-metal-catalyzed reactions represent one of the most challenging routes for the preparation of heterocyclic compounds [1][2][3][4][5]. Methodologies

• . During our studies aimed at the synthesis of complex heterocyclic systems by intramolecular transition-metal-catalyzed protocols [20][21][22][23][24][25][26][27][28][29][30][31][32], we reported an arylative Pd-catalyzed cyclization of N-allyl-pyrrole-2-carboxamides, affording pyrrolo[1,2-a]pyrazines or