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C–H Activation

The possibility of direct introduction of a new functionality (or a new C–C bond) via direct C–H bond transformation is a highly attractive strategy in covalent synthesis. The range of substrates is virtually unlimited, including hydrocarbons, complex organic compounds of small molecular weight, and synthetic and biological polymers. Below is a list of recent articles on this topic. For a review, see

  1. Xiao Chen, Keary M. Engle, Dong-Hui Wang, Jin-Quan Yu*
    Palladium(II)-Catalyzed C–H Activation/C–C Cross-Coupling Reactions: Versatility and Practicality
    Angew. Chem. 2009, 121, 5196–5217; Angew. Chem. Int. Ed. 2009, 48, 5094–5115

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Recent Articles

Chunxiang Wang, Dongping Wang, Hao Yan, Haolong Wang, Bin Pan, Xiaoyi Xin, Xincheng Li, Fan Wu, Boshun Wan
Rhodium-Catalyzed Cyclization of Diynes with Nitrones: A Formal [2+2+5] Approach to Bridged Eight-Membered Heterocycles [Communication]

Rhodium-Catalyzed Cyclization of Diynes with Nitrones: A Formal [2+2+5] Approach to Bridged Eight-Membered Heterocycles

Five-atom building unit: N-aryl-substituted nitrones were employed as five-atom coupling partners in the rhodium-catalyzed cyclization with diynes. In this reaction, the nitrone moiety served as a directing group for the catalytic C-H activation of the N-aryl ring. This formal [2+2+5] approach allows rapid access to bridged eight-membered heterocycles with broad substrate scope.

Angew. Chem. Int. Ed., September 12, 2014, DOI: 10.1002/anie.201407394

Chiral Counteranion Strategy for Asymmetric Oxidative C(sp3)-H/C(sp3)-H Coupling: Enantioselective α-Allylation of Aldehydes with Terminal Alkenes

Go with the combo: The title reaction is realized by combining asymmetric counteranion catalysis and palladium-catalyzed allylic C-H activation. This method tolerates a wide scope of α-branched aromatic aldehydes and terminal alkenes, thus affording allylation products in high yields and with good to excellent levels of enantioselectivity.

Angew. Chem. Int. Ed., September 12, 2014, DOI: 10.1002/anie.201408199

Laura Rubio-Pérez, Manuel Iglesias, Ricardo Castarlenas, Victor Polo, Jesús J. Pérez-Torrente, Luis A. Oro
Selective C-H Bond Functionalization of 2-(2-Thienyl)pyridine by a Rhodium N-Heterocyclic Carbene Catalyst [Full Paper]

Selective C-H Bond Functionalization of 2-(2-Thienyl)pyridine by a Rhodium N-Heterocyclic Carbene Catalyst

For your C-H bond only: [Rh(μ-Cl)(H)2(IPr)]2 (IPr=1,3-bis-(2,6-diisopropylphenyl)imidazol-2-ylidene) catalyzes the selective functionalization of 2-(2-thienyl)pyridine efficiently with a range of alkenes and internal alkynes. A catalytic cycle is proposed on the basis of the identification of key reaction intermediates and the study of their reactivity by NMR spectroscopy.

ChemCatChem, September 12, 2014, DOI: 10.1002/cctc.201402507

Sulfonamide-Promoted Palladium(II)-Catalyzed Alkylation of Unactivated Methylene C(sp3)-H Bonds with Alkyl Iodides

Branching off: The title reaction of unactivated β-methylene C(sp3)-H bonds of α-amino acid substrates with alkyl iodides is described. The C(alkyl)– C(alkyl) bond-forming reaction proceeds in good yields, and by using sequential reactions β-branched amino acids can be obtained.

Angew. Chem. Int. Ed., September 11, 2014, DOI: 10.1002/anie.201407848

Jianbin Chen, Kishore Natte, Anke Spannenberg, Helfried Neumann, Matthias Beller, Xiao-Feng Wu
Palladium-Catalyzed Carbonylative [3+2+1] Annulation of N-Aryl-Pyridine-2-Amines with Internal Alkynes by C-H Activation: Facile Synthesis of 2-Quinolinones [Communication]

Palladium-Catalyzed Carbonylative [3+2+1] Annulation of N-Aryl-Pyridine-2-Amines with Internal Alkynes by C-H Activation: Facile Synthesis of 2-Quinolinones

Carbonylative C-H activation: A procedure for the synthesis of highly substituted 2-quinolinones has been developed. By this newly developed approach, 2-quinolinone derivatives were prepared in moderate to good yields by carbonylative [3+2+1] annulation of N-aryl-pyridine-2-amines and internal alkynes by C-H activation (see scheme).

Chem. Eur. J., September 11, 2014, DOI: 10.1002/chem.201404462

Alexander G. O'Brien, Akinobu Maruyama, Yasuhide Inokuma, Makoto Fujita, Phil S. Baran, Donna G. Blackmond
Radical C-H Functionalization of Heteroarenes under Electrochemical Control [Communication]

Radical C-H Functionalization of Heteroarenes under Electrochemical Control

Electrochemical reactions are shown to be effective for the C-H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions and of interest in medicinal chemistry. Monitoring reaction progress under electrochemical conditions provides mechanistic insight into the C-H functionalization process.

Angew. Chem. Int. Ed., September 10, 2014, DOI: 10.1002/anie.201407948

Niles J. Gunsalus, Michael M. Konnick, Brian G. Hashiguchi, Roy A. Periana
Discrete Molecular Catalysts for Methane Functionalization [Review]

Jianbin Chen, Lin He, Kishore Natte, Helfried Neumann, Matthias Beller, Xiao-Feng Wu
Palladium@Cerium(IV) Oxide-Catalyzed Oxidative Synthesis of N-(2-Pyridyl)indoles via C-H Activation Reaction [Communication]

Upendra Sharma, Rajesh Kancherla, Togati Naveen, Soumitra Agasti, Debabrata Maiti
Palladium-Catalyzed Annulation of Diarylamines with Olefins through C-H Activation: Direct Access to N-Arylindoles [Communication]

Palladium-Catalyzed Annulation of Diarylamines with Olefins through C-H Activation: Direct Access to N-Arylindoles

No group help needed: A palladium-catalyzed dehydrogenative coupling between diarylamines and olefins has been discovered for the synthesis of substituted indoles. This intermolecular annulation approach incorporates readily available olefins and obviates the need of any additional directing group. An ortho palladation, olefin coordination, and β-migratory insertion sequence has been proposed for the generation of an olefinated intermediate.

Angew. Chem. Int. Ed., September 9, 2014, DOI: 10.1002/anie.201406284

Peng Yu, Jin-Shun Lin, Lei Li, Sheng-Cai Zheng, Ya-Ping Xiong, Li-Jiao Zhao, Bin Tan, Xin-Yuan Liu
Enantioselective C-H Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene [Communication]

Enantioselective C-H Bond Functionalization Triggered by Radical Trifluoromethylation of Unactivated Alkene

En route: The title redox-neutral reaction provides a convenient route to valuable enantioenriched trifluoromethylated N,O-aminals in good to excellent yields and with excellent regio-, chemo-, and enantioselectivity. The reaction features a CuI/Brønsted acid system and broad substrate scope.

Angew. Chem. Int. Ed., September 8, 2014, DOI: 10.1002/anie.201405401

Ruthenium(II)-Catalyzed C-H Activation with Isocyanates: A Versatile Route to Phthalimides

A convenient route to phthalimide: A convergent method for the ruthenium(II)-catalyzed imidation of easily accessible benzamides by C-H functionalization was developed (see scheme). The methodology was successfully applied to the preparation of synthetically challenging unsymmetrical heteroaromatic diamides and proved amenable to a step-economic synthesis of a potent COX-2 enzyme inhibitor.

Chem. Eur. J., September 8, 2014, DOI: 10.1002/chem.201404261

Rowan D. Young
Characterisation of Alkane σ-Complexes [Minireview]

Characterisation of Alkane σ-Complexes

The coordination of alkanes to metal centers is a complex matter! Advances in synthetic strategies to produce alkane σ-complexes, and ever more detailed analyses of such complexes, is leading to an understanding of how alkanes bind to specific metal centers. Such analysis is vital in understanding selectivity in C-H activation reactions.

Chem. Eur. J., September 5, 2014, DOI: 10.1002/chem.201403485

Nikolay S. Sitnikov, Antonina S. Kokisheva, Georgy K. Fukin, Jörg-Martin Neudörfl, Hannah Sutorius, Aram Prokop, Valery V. Fokin, Hans-Günther Schmalz, Alexey Yu. Fedorov
Synthesis of Indole-Derived Allocolchicine Congeners through Pd-Catalyzed Intramolecular C-H Arylation Reaction [Full Paper]

Synthesis of Indole-Derived Allocolchicine Congeners through Pd-Catalyzed Intramolecular C-H Arylation Reaction

The synthesis of indole-derived structural analogs of natural antimitotic agent allocolchicine is reported. In a key step, an intramolecular Pd-catalyzed C–H arylation reaction serves to construct the polycyclic ring system, by connecting the two electron-rich arene fragments.

Eur. J. Org. Chem., September 4, 2014, DOI: 10.1002/ejoc.201402850

Spiroacetal Formation through Telescoped Cycloaddition and Carbon–Hydrogen Bond Functionalization: Total Synthesis of Bistramide A

Actin' out: Spiroacetals can be prepared from aldehydes and functionalized dienes through a convergent, telescoped sequence of cycloaddition, oxidative C-H bond cleavage, and acid treatment. The functional-group tolerance and facile accessibility of the components render this protocol suitable for the synthesis of structurally complex natural products such as the actin-binding cytotoxin bistramide A.

Angew. Chem. Int. Ed., September 4, 2014, DOI: 10.1002/anie.201406819

Unexpected Cyclization of Tritylamines Promoted by Copper Salt through C-H and C-N Bond Cleavages to Produce Acridine Derivatives

Construction of 9-arylacridines was achieved through a new copper-mediated dehydrogenative cyclization of tritylamines involving two C-H and one C-N bond cleavages. Some of obtained acridine derivatives exhibited intense fluorescence in the solid state (see scheme).

Chem. Eur. J., September 4, 2014, DOI: 10.1002/chem.201404656

Matthijs Ruitenbeek, Bert M. Weckhuysen
A Radical Twist to the Versatile Behavior of Iron in Selective Methane Activation [Highlight]

A Radical Twist to the Versatile Behavior of Iron in Selective Methane Activation

Things go better without coke! The selective activation of methane and its direct conversion into light olefins and aromatic compounds remains a formidable challenge. Recent work shows that a catalyst material consisting of lattice-confined single iron atoms is very active and selective in the direct, nonoxidative conversion of methane into ethylene, benzene, and naphthalene without the formation of coke deposits.

Angew. Chem. Int. Ed., September 4, 2014, DOI: 10.1002/anie.201407109

Catalytic Asymmetric Functionalization of Aromatic C-H Bonds by Electrophilic Trapping of Metal-Carbene-Induced Zwitterionic Intermediates

Caught in a trap: The title reaction of N,N-disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α-diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. Efficient electrophilic trapping of the metal-carbene-induced zwitterionic intermediate is crucial for the enantiocontrol under RhII/chiral phosphoric acid (PPA) co-catalysis.

Angew. Chem. Int. Ed., September 4, 2014, DOI: 10.1002/anie.201406492

Palladium(0)-Catalyzed Heck Reaction/C-H Activation/Amination Sequence with Diaziridinone: A Facile Approach to Indolines

Good form: Indolines are important moieties present in various biologically significant molecules. Described is the title sequence for forming indolines with di-tert-butyldiaziridinone. The reaction process likely proceeds via a pallada(II)cycle, which is converted into an indoline by oxidative addition to the diaziridinone and two subsequent C-N bond formations.

Angew. Chem. Int. Ed., September 4, 2014, DOI: 10.1002/anie.201405365

Yingjun Zhu, Michaela Bauer, Jasper Ploog, Lutz Ackermann
Late-Stage Diversification of Peptides by Metal-Free C-H Arylation [Communication]

Late-Stage Diversification of Peptides by Metal-Free C-H Arylation

Metal-free direct arylations of engineered indole-3-acetamides set the stage for the late-stage diversifications of highly functionalized peptides under mild reaction conditions.

Chem. Eur. J., August 28, 2014, DOI: 10.1002/chem.201404603

Yoshihiro Oonishi, Adrián Gómez-Suárez, Anthony R. Martin, Yusuke Makida, Alexandra M. Z. Slawin, Steven P. Nolan
[Au]/[Pd] Multicatalytic Processes: Direct One-Pot Access to Benzo[c]chromenes and Benzo[b]furans [Communication]

[Au]/[Pd] Multicatalytic Processes: Direct One-Pot Access to Benzo[c]chromenes and Benzo[b]furans

Very neat reactions! A new strategy for the synthesis of benzo[c]chromenes and benzo[b]furans from commercially available starting materials is reported. This two-step, one-pot strategy consists in a gold-catalyzed hydrophenoxylation reaction followed by Pd-catalyzed C-H activation or Mizoroki–Heck reactions.

Chem. Eur. J., August 28, 2014, DOI: 10.1002/chem.201404630

Katharina Neufeld, Birgit Henßen, Jörg Pietruszka
Enantioselective Allylic Hydroxylation of ω-Alkenoic Acids and Esters by P450 BM3 Monooxygenase [Communication]

Enantioselective Allylic Hydroxylation of ω-Alkenoic Acids and Esters by P450 BM3 Monooxygenase

Modern biocatalysts on the rise: The P450 BM3 monooxygenase mutant A74G/L188Q catalyzes the enantioselective allylic hydroxylation of ω-alkenoic acids and esters under mild conditions using O2 as an oxidant. This reaction offers access to important chiral building blocks for the synthesis of biologically active compounds and demonstrates the highest chemo- and enantioselectivity observed to date for the C-H oxidation of acyclic terminal olefins.

Angew. Chem. Int. Ed., August 27, 2014, DOI: 10.1002/anie.201403537

C(sp3)-H Activation without a Directing Group: Regioselective Synthesis of N-Ylide or N-Heterocyclic Carbene Complexes Controlled by the Choice of Metal and Ligand

Which C-H bond reacts? N-Ylide complexes of Ir were generated by α-C(sp3--H activation with [Cp*IrCl2]2 and NaOAc. The reaction of an α-imidazolium ester is a rare example of a C-H activation where the site selectivity can be controlled by the choice of metal and ligand; DFT calculations revealed that the N-ylide complex is the kinetic product of an ambiphilic C-H activation, in which the acetate ligand plays the dominant role (see scheme).

Chem. Eur. J., August 27, 2014, DOI: 10.1002/chem.201403860

Anna M. Rydzik, Ivanhoe K. H. Leung, Grazyna T. Kochan, Michael A. McDonough, Timothy D. W. Claridge, Christopher J. Schofield
Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids [Communication]

Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids

Thinking outside the BBOX: γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate (2OG)-dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers.

Angew. Chem. Int. Ed., August 27, 2014, DOI: 10.1002/anie.201406125

A Common Synthetic Protocol for the Cyclic and Acyclic Core of Migrastatin, Isomigrastatin, and Dorrigocin via a Chiral β-Hydroxy-γ-butyrolactone Intermediate

The synthesis of a key intermediate chiral β-hydroxy-γ-butyrolactone (A) by PdII-catalysed stereoselective allylic C–H oxidation is reported. A common synthetic route to transform this intermediate into key building blocks for the synthesis of migrastatin family members has been developed.

Eur. J. Org. Chem., August 26, 2014, DOI: 10.1002/ejoc.201402830

Fanzhi Yang, Karsten Rauch, Katharina Kettelhoit, Lutz Ackermann
Aldehyde-Assisted Ruthenium(II)-Catalyzed C-H Oxygenations [Communication]

Aldehyde-Assisted Ruthenium(II)-Catalyzed C-H Oxygenations

The weakest link: Challenging aryl C-H oxygenations with very weakly coordinating aldehydes proceed chemoselectively in the presence of versatile ruthenium(II) catalysts under mild reaction conditions. This transformation features an ample substrate scope and excellent positional selectivity.

Angew. Chem. Int. Ed., August 26, 2014, DOI: 10.1002/anie.201405647

Ryo Murakami, Kiyoshi Tsunoda, Tomohiro Iwai, Masaya Sawamura
Stereoselective C-H Borylations of Cyclopropanes and Cyclobutanes with Silica-Supported Monophosphane–Ir Catalysts [Communication]

Stereoselective C-H Borylations of Cyclopropanes and Cyclobutanes with Silica-Supported Monophosphane–Ir Catalysts

Heteroatom-directed C-H borylations of small-ring carbocycles, such as cyclopropanes and cyclobutanes, were achieved with silica-supported monophosphane–Ir catalysts (see scheme). Borylation occurred at the C-H bonds located γ to the directing N or O atoms with exceptional cis stereoselectivity relative to the directing groups.

Chem. Eur. J., August 22, 2014, DOI: 10.1002/chem.201404362

Woo-Jin Yoo, Arata Tanoue, Shū Kobayashi
Zinc(II) Hexachloroantimonate-Catalyzed Oxidative Allylation of Glycine Derivatives [Communication]

Zinc(II) Hexachloroantimonate-Catalyzed Oxidative Allylation of Glycine Derivatives

Proof-of-concept for the use of metal antimonates as bifunctional catalysts for oxidative coupling reactions is described. A well-defined zinc(II) antimonate salt enables the α-functionalization of glycine derivatives through a sequential aerobic oxidation-allylation reaction, in which the antimonate anion is responsible for the aerobic oxidation and the zinc cation acts as a Lewis acid for the allylation reaction. EWG=electron-withdrawing group; PMP=p-methoxyphenyl.

Asian J. Org. Chem., August 21, 2014, DOI: 10.1002/ajoc.201402108

Rhodium(III)-Catalyzed Intramolecular Redox-Neutral Annulation of Tethered Alkynes: Formal Total Synthesis of (±)-Goniomitine

C-H activation: A RhIII-catalyzed intramolecular redox-neutral atom-economic annulation of a tethered alkyne has been developed to efficiently construct 2-amidealkyl indoles with completely reversed regioselectivity by a C-H activation pathway (see scheme). A one-pot synthesis of pyrido[1,2-a]indoles has also been developed and applied to a highly efficient formal total synthesis of (±)-goniomitine.

Chem. Eur. J., August 21, 2014, DOI: 10.1002/chem.201403973

C-H Functionalization/Asymmetric Michael Addition Cascade Enabled by Relay Catalysis: Metal Carbenoid used for C-C Bond Formation

Square deal: A combination of either ruthenium(II) or rhodium(II) complexes and quinine-derived squaramide enables 3-diazooxindoles, indole, and nitroalkenes to undergo a highly efficient asymmetric three-component reaction. Based on this metal/organo relay catalysis, a total synthesis of (−)-folicanthine was accomplished in seven steps with 14.5 % overall yield.

Angew. Chem. Int. Ed., August 21, 2014, DOI: 10.1002/anie.201406098

Rhodium(III)-Catalyzed C-C and C-O Coupling of Quinoline N-Oxides with Alkynes: Combination of C-H Activation with O-Atom Transfer

A chance meeting: A rhodium(III)-catalyzed redox-neutral coupling of quinoline N-oxides with alkynes has been realized, thus leading to the synthesis of α-substituted acetophenones. This system integrates C-H activation with O-atom transfer.

Angew. Chem. Int. Ed., August 14, 2014, DOI: 10.1002/anie.201406747

Synthesis of Urchin-Like FeF2 Nanoarchitectures and Their Conversion into Three-Dimensional Urchin-Like Mesoporous α-Fe2O3 Nanoarchitectures for Methane Activation

Novel urchin-like FeF2 nanoarchitectures have been fabricated by an unconventional nonhomogeneous ionic liquid/diphenyl ether solvothermal method and converted into 3D urchin-like mesoporous α-Fe2O3 nanoarchitectures by solid-state thermal annealing. The α-Fe2O3 nanoarchitectures exhibit good catalytic properties in methane activation reactions.

Eur. J. Inorg. Chem., August 11, 2014, DOI: 10.1002/ejic.201402152

Michael M. Konnick, Brian G. Hashiguchi, Deepa Devarajan, Nicholas C. Boaz, T. Brent Gunnoe, John T. Groves, Niles Gunsalus, Daniel H. Ess, Roy A. Periana
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex [Communication]

Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex

Gas up: Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate (TFA) esters is achieved by a homogeneous hypervalent iodine(III) complex in non-superacidic solvent (HTFA). The reaction is highly selective, and for ethane, greater than 0.5 M Et-TFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism.

Angew. Chem. Int. Ed., August 11, 2014, DOI: 10.1002/anie.201406185

K. C. Nicolaou, Philipp Heretsch, Abdelatif ElMarrouni, Christopher R. H. Hale, Kiran K. Pulukuri, Avinash K. Kudva, Vivek Narayan, K. Sandeep Prabhu
Total Synthesis of Δ12-Prostaglandin J3, a Highly Potent and Selective Antileukemic Agent [Communication]

Total Synthesis of Δ12-Prostaglandin J3, a Highly Potent and Selective Antileukemic Agent

Leukemia ablator: The naturally occurring and highly potent and selective antileukemic agent Δ12-prostaglandin J312-PGJ3) has been assembled through a catalytic, asymmetric, and convergent strategy. The total synthesis renders this precious but rare substance readily available for thorough biological investigations and opens the way for analogue design, synthesis, and biological evaluation.

Angew. Chem. Int. Ed., August 5, 2014, DOI: 10.1002/anie.201404917

Ming Shang, Shang-Zheng Sun, Hong-Li Wang, Brian N. Laforteza, Hui-Xiong Dai, Jin-Quan Yu
Exceedingly Fast Copper(II)-Promoted ortho C-H Trifluoromethylation of Arenes using TMSCF3 [Communication]

Exceedingly Fast Copper(II)-Promoted ortho C-H Trifluoromethylation of Arenes using TMSCF3

CF3 installation: The direct ortho-trifluoromethylation of arenes including heteroarenes with TMSCF3 has been accomplished by a copper(II)-promoted C-H activation reaction. Mechanistic investigations are consistent with the involvement of C-H activation rather than a simple electrophilic aromatic substitution as the key step. DG=directing group, TMS=trimethylsilyl.

Angew. Chem. Int. Ed., August 5, 2014, DOI: 10.1002/anie.201404822

Brendan M. Monks, Erin R. Fruchey, Silas P. Cook
Iron-Catalyzed C(sp2)-H Alkylation of Carboxamides with Primary Electrophiles [Communication]

Iron-Catalyzed C(sp2)-H Alkylation of Carboxamides with Primary Electrophiles

The direct ortho alkylation of 8-aminoquinoline-based aryl amides was achieved with primary alkyl bromides in high yields in the presence of an iron catalyst, 1,2-bis(diphenylphosphino)ethane (dppe), and PhMgBr in 2-MeTHF.

Angew. Chem. Int. Ed., August 3, 2014, DOI: 10.1002/anie.201406594

Wajid Ali, Srimanta Guin, Saroj Kumar Rout, Anupal Gogoi, Bhisma K. Patel
Thioesterification of Alkylbenzenes with Thiols via Copper- Catalyzed Cross-Dehydrogenative Coupling without a Directing Group [Full Paper]

Yuehui Li, Tao Yan, Kathrin Junge, Matthias Beller
Catalytic Methylation of C-H Bonds Using CO2 and H2 [Communication]

Catalytic Methylation of C-H Bonds Using CO2 and H2

Capturing: Carbon dioxide in the presence of H2 is shown to be an efficient methylating reagent for carbon nucleophiles such as 2-substituted indoles, pyrroles, and electron-rich arenes. Experimental data support the formal capture of formaldehyde. acac=acetylacetonate, triphos=1,1,1-tris(diphenylphosphinomethyl)ethane.

Angew. Chem. Int. Ed., July 30, 2014, DOI: 10.1002/anie.201405779

Shao-Jie Lou, Dan-Qian Xu, Zhen-Yuan Xu
Mild and Versatile Nitrate-Promoted C-H Bond Fluorination [Communication]

Mild and Versatile Nitrate-Promoted C-H Bond Fluorination

Nitrate makes it possible: A novel and facile method for C-H bond fluorination entails remarkably mild reaction conditions (close to room temperature in most cases). Both aromatic and olefinic C(sp2)-H bonds were selectively fluorinated in the presence of a catalytic amount of inexpensive and nontoxic nitrate as the promoter.

Angew. Chem. Int. Ed., July 14, 2014, DOI: 10.1002/anie.201404423

Davide Ravelli, Matteo Zoccolillo, Mariella Mella, Maurizio Fagnoni
Photocatalytic Synthesis of Oxetane Derivatives by Selective C-H Activation [Communication]

Copper-Promoted Site-Selective Acyloxylation of Unactivated C(sp3)-H Bonds

Getting promoted: The site-selective acyloxylation of aliphatic amides was achieved via a copper-promoted C(sp3)-H bond functionalization process directed by a bidentate ligand. The reaction showed a great preference for activating C-H bonds of β-methyl groups over those of γ-methyl and unactivated methylene groups.

Chem. Asian J. 2014, 9, No. 10, 2736-2739

Aniline Carbamates: A Versatile and Removable Motif for Palladium-Catalyzed Directed C-H Activation

G'day, (carba)mate! A new removable directing group for sp2 C-H activation, the aniline carbamate, is examined in detail. Its utility as a directing group is demonstrated by the ortho-arylation of aniline derivatives under PdII catalysis, with iodonium salts as aryl donors and oxidants. Excellent regio- and chemoselectivity were observed. The directing group can also be easily removed to yield 2-aminobiaryl products (see scheme).

Chem. Eur. J. 2014, 20, No. 38, 12066-12070

Palladium-Catalyzed Cascade C-H Trifluoroethylation of Aryl Iodides and Heck Reaction: Efficient Synthesis of ortho-Trifluoroethylstyrenes

The palladium-catalyzed selective C-H bond trifluoroethylation of aryl iodides allows for an efficient synthesis of a variety of ortho-trifluoroethyl-substituted styrenes. Preliminary mechanistic studies indicate that the reaction might proceed through rate-determining oxidative addition of CF3CH2I to a palladacycle.

Angew. Chem. Int. Ed. 2014, 53, No. 38, 10174-10178

Cobalt-Catalyzed, Aminoquinoline-Directed C(sp2)-H Bond Alkenylation by Alkynes

In the air: Excellent functional-group tolerance is observed in the title reaction, and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs Co(OAc)2·4 H2O as the catalyst, Mn(OAc)2 as the co-catalyst, and oxygen (from air) as the terminal oxidant. Piv=pivalate.

Angew. Chem. Int. Ed. 2014, 53, No. 38, 10209-10212

Combining Rhodium and Photoredox Catalysis for C-H Functionalizations of Arenes: Oxidative Heck Reactions with Visible Light

Much milder and environmentally friendly reaction conditions can be used for oxidative Heck reactions through the combined use of rhodium and redox catalysis. This allows the rhodium complex to be catalytically regenerated. A broad range of substrates was tolerated in the reaction and afforded different amides in good to very good yields.

Angew. Chem. Int. Ed. 2014, 53, No. 38, 10228-10231

Michael C. Haibach, Nicholas Lease, Alan S. Goldman
Catalytic Cleavage of Ether C-O Bonds by Pincer Iridium Complexes [Communication]

Catalytic Cleavage of Ether C-O Bonds by Pincer Iridium Complexes

A catalyst for ether direction: Cleavage of the alkyl C-O bond of aryl ethers is catalyzed by pincer Ir catalysts, without the need for additional reagents, including H2. The corresponding phenols are generated in up to 99 % conversion, with reaction times as short as 1 hour.

Angew. Chem. Int. Ed. 2014, 53, No. 38, 10160-10163

Chao Wang, Changpeng Chen, Jingyu Zhang, Jian Han, Qian Wang, Kun Guo, Pei Liu, Mingyu Guan, Yingming Yao, Yingsheng Zhao
Easily Accessible Auxiliary for Palladium-Catalyzed Intramolecular Amination of C(sp2)-H and C(sp3)-H Bonds at δ- and ε-Positions [Communication]

Easily Accessible Auxiliary for Palladium-Catalyzed Intramolecular Amination of C(sp2)-H and C(sp3)-H Bonds at δ- and ε-Positions

Remote access: The first application of an oxalyl amide to direct C-H functionalizations at remote positions is reported. The results show both C(sp2)-H and C(sp3)-H bonds at δ- and ε-positions are effectively activated, thus giving tetrahydroquinolines, benzomorpholines, pyrrolidines, and indolines in moderate to excellent yields by palladium-catalyzed intramolecular C-H amination.

Angew. Chem. Int. Ed. 2014, 53, No. 37, 9884-9888

Jayachandran Jayakumar, Kanniyappan Parthasarathy, Yi-Hsiang Chen, Tai-Hua Lee, Shih-Ching Chuang, Chien-Hong Cheng
One-Pot Synthesis of Highly Substituted Polyheteroaromatic Compounds by Rhodium(III)-Catalyzed Multiple C-H Activation and Annulation [Communication]

One-Pot Synthesis of Highly Substituted Polyheteroaromatic Compounds by Rhodium(III)-Catalyzed Multiple C-H Activation and Annulation

Activated and annulated: A rhodium-catalyzed one-pot synthesis of highly substituted polyheteroaromatic compounds from N-hydroxybenzamidines and alkynes is described. This reaction likely proceeds through multiple C-H bond activation and annulation.

Angew. Chem. Int. Ed. 2014, 53, No. 37, 9889-9892

Michael Parmentier, Thomas Hartung, Andreas Pfaltz, Dieter Muri
Iridium-Catalyzed H/D Exchange: Ligand Complexes with Improved Efficiency and Scope [Full Paper]

Iridium-Catalyzed H/D Exchange: Ligand Complexes with Improved Efficiency and Scope

Uses beyond asymmetric catalysis: Iridium complexes with a wide variety of N,P-ligands were explored in hydrogen isotope exchange reactions (see scheme; pyr.=pyridine). Complexes with electron-rich ligands were found to be highly reactive, leading to efficient deuterium incorporation even in compounds bearing only weakly coordinating directing groups.

Chem. Eur. J. 2014, 20, No. 36, 11496-11504

Johannes Schranck, Anis Tlili, Matthias Beller
Functionalization of Remote C-H Bonds: Expanding the Frontier [Highlight]

Functionalization of Remote C-H Bonds: Expanding the Frontier

Novel tool set: New methodologies for the functionalization of remote C-H bonds have been developed recently. In diverse approaches high selectivities are achieved for the functionalization of less reactive C(sp2)-H as well as C(sp3)-H bonds distal to any substituents.

Angew. Chem. Int. Ed. 2014, 53, No. 36, 9426-9428

Lando P. Wolters, Willem-Jan van Zeist, F. Matthias Bickelhaupt
New Concepts for Designing d10-M(L)n Catalysts: d Regime, s Regime and Intrinsic Bite-Angle Flexibility [Full Paper]

New Concepts for Designing d10-M(L)n Catalysts: d Regime, s Regime and Intrinsic Bite-Angle Flexibility

d or s regime? That is the question! A catalyst's orbital electronic regime (see illustration) and bite-angle flexibility are proposed as unifying concepts that serve a more rational design of catalysts. They emerge from quantum-chemical activation strain analyses of 72 different d10-M(L)n model catalyst mediated C-H bond-activation reactions.

Chem. Eur. J. 2014, 20, No. 36, 11370-11381

Chemoselective Phototransformation of C-H Bonds on a Polymer Surface through a Photoinduced Cerium Recycling Redox Reaction

Recycling itself! A bio-inspired artificial recycling reaction system has been constructed based on the strategic design of a photoinduced Ce3+–Ce4+ recycling redox reaction, leading to efficient photorecovery of reactants to achieve a reactant-loss-free direct transformation of alkyl C-H bonds on polymer surfaces to form small-molecule groups and polymer brushes (see scheme).

Chem. Eur. J. 2014, 20, No. 36, 11421-11427

Da-Gang Yu, Francisco de Azambuja, Tobias Gensch, Constantin G. Daniliuc, Frank Glorius
The C-H Activation/1,3-Diyne Strategy: Highly Selective Direct Synthesis of Diverse Bisheterocycles by RhIII Catalysis [Communication]

The C-H Activation/1,3-Diyne Strategy: Highly Selective Direct Synthesis of Diverse Bisheterocycles by RhIII Catalysis

Di-verse: The use of the C-H activation/1,3-diyne general strategy allowed the challenges of selectivity (chemo-, regio-, and mono-/diannulation) to be overcome. This allowed direct construction of diverse polysubstituted bisheterocycles, which are highly important but difficult to access, through the formation of four strategic bonds with high efficiency and high selectivity.

Angew. Chem. Int. Ed. 2014, 53, No. 36, 9650-9654

Grzegorz Filipczyk, Alexander Hildebrandt, Ulrike Pfaff, Marcus Korb, Tobias Rüffer, Heinrich Lang
Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures [Short Communication]

Combining Cobalt-Assisted Alkyne Cyclotrimerization and Ring Formation through C–H Bond Activation: A “One-Pot” Approach to Complex Multimetallic Structures

A straightforward one-pot synthetic method including cyclotrimerization, C–H activation, and ring formation to novel hexaferrocenylbenzene is discussed. The electrochemical and spectro-electrochemical behavior as well as a mechanism for the formation of the title compound is reported.

Eur. J. Inorg. Chem. 2014, No. 26, 4258-4262

A Unified Strategy Towards N-Aryl Heterocycles by a One-Pot Copper-Catalyzed Oxidative C–H Amination of Azoles

An efficient one-pot synthesis of N-aryl heterocycles by a Cu-catalysed double C–N bond formation is reported. This strategy involves a CuI-catalysed C–N bond-forming reaction between azoles and electron-deficient bromopyridines followed by an intramolecular sp2 C–H amination.

Eur. J. Org. Chem. 2014, No. 27, 5986-5997

Frédéric Liron, Julie Oble, Mélanie M. Lorion, Giovanni Poli
Direct Allylic Functionalization Through Pd-Catalyzed C–H Activation [Microreview]

Direct Allylic Functionalization Through Pd-Catalyzed C–H Activation

This review outlines some selected examples and present challenges relating to palladium-catalyzed direct allylic functionalization. This old reaction, ignored for many years, is enjoying a new age.

Eur. J. Org. Chem. 2014, No. 27, 5863-5883

Wenjie Liu, Shaohua Wang, Qi Zhang, Jingwen Yu, Jiahe Li, Zhiwei Xie, Hua Cao
Regioselective C3 Alkenylation of 4 H-pyrido[1,2-a]pyrimidin-4-ones via Palladium-Catalyzed C-H Activation [Communication]

Regioselective C3 Alkenylation of 4 H-pyrido[1,2-a]pyrimidin-4-ones via Palladium-Catalyzed C-H Activation

Active ingredient: A new efficient method for the direct alkenylation of 4H-pyrido[1,2-a]pyrimidin-4-ones via palladium-catalyzed C-H bond activation has been developed. This transformation presents a useful approach to functionalize 4H-pyrido[1,2-a]pyrimidin-4-ones, which are privileged structures in many bioactive molecules and versatile synthetic blocks.

Chem. Asian J. 2014, 9, No. 09, 2436-2439

A Practical Approach for the Oxidation of Unactivated Csp3-H Bonds with o-Nitro(diacetoxyiodo)benzene as an Efficient Hypervalent Iodine(III)-Based Oxidizing Agent

A bit hyper: A practical approach for the oxidation of unactivated Csp3-H bonds by o-nitro(diacetoxyiodo)benzene is presented. The nitro group coordinates to the adjacent iodine center through dipolar interaction, which leads to a single substitution of the acetate ligand by tert-butyl hydroperoxide (TBHP). As a result, a strong iodanyl radical is formed, which can activate the inert Csp3-H bonds in a highly efficient manner.

Asian J. Org. Chem. 2014, 3, No. 09, 932-935

Regiospecific Synthesis of Substituted 2-Nitrobenzaldehydes from Benzaldehydes through Palladium-Catalyzed Chelation-Assisted C–H Nitration

An efficient and general method for the regiospecific synthesis of substituted 2-nitrobenzaldehydes from related benzaldehydes has been developed. The approach involves palladium-catalyzed chelation-assisted C–H nitration as the key step, and enables regiospecific nitration of C–H bonds free from the effect of orientation rules.

Eur. J. Org. Chem. 2014, No. 26, 5827-5835

Chihiro Tsukano, Nobusuke Muto, Iderbat Enkhtaivan, Yoshiji Takemoto
Synthesis of Pyrrolophenanthridine Alkaloids Based on C(sp3)-H and C(sp2)-H Functionalization Reactions [Full Paper]

Synthesis of Pyrrolophenanthridine Alkaloids Based on C(sp3)-H and C(sp2)-H Functionalization Reactions

Ring expansion: The alkaloids assoanine (1), pratosine (2), hippadine (3), and dehydroanhydrolycorine (4), which belong to the pyrrolophenanthridine family of alkaloids, have been successfully synthesized by using C-H activation chemistry. The tetracyclic skeletons are constructed in a stepwise manner by C(sp3)-H functionalization and a Catellani reaction involving C(sp2)-H functionalization.

Chem. Asian J. 2014, 9, No. 09, 2628-2634

Chen-Hsun Hung, Parthasarathy Gandeepan, Chien-Hong Cheng
Ruthenium(II)-Catalyzed C-H Bond Activation: An Efficient Route toward Indenamines [Full Paper]

Ruthenium(II)-Catalyzed C-H Bond Activation: An Efficient Route toward Indenamines

Atomic bean counters succeed! An efficient and atom-economical method for the synthesis of substituted indenamines from N-tosylarylimines and alkynes via ruthenium(II)-catalyzed C-H bond activation and annulation is described.

ChemCatChem 2014, 6, No. 09, 2692-2697

M. Angeles Fuentes, Andrea Olmos, Bianca K. Muñoz, Kane Jacob, M. Elena González-Núñez, Rossella Mello, Gregorio Asensio, Ana Caballero, Michel Etienne, Pedro J. Pérez
Catalytic Functionalization of Methane and Light Alkanes in Supercritical Carbon Dioxide [Full Paper]

Catalytic Functionalization of Methane and Light Alkanes in Supercritical Carbon Dioxide

Methane activation: Methane can be catalytically converted into ethyl propionate upon reaction with ethyl diazoacetate in the presence of highly fluorinated silver complexes as catalysts and by using supercritical carbon dioxide; (scCO2) as the reaction medium (see scheme; TOF=time of flight).

Chem. Eur. J. 2014, 20, No. 35, 11013-11018

Catalytic Borylation of SCF3-Functionalized Arenes by Rhodium(I) Boryl Complexes: Regioselective C-H Activation at the ortho-Position

SCF3 building blocks: A unique reaction route allows access to SCF3-functionalized arenes, which are borylated at the ortho-position. The functionalization proceeds by C-H borylation with [Rh(Bpin)(PEt3)3] (pin=pinacolato), and the SCF3 group likely serves as directing group. The generated borylated SCF3 compounds are versatile building blocks for further transformations.

Angew. Chem. Int. Ed. 2014, 53, No. 35, 9311-9315

Simon Janody, Rodolphe Jazzar, Arnaud Comte, Philipp M. Holstein, Jean-Pierre Vors, Mark J. Ford, Olivier Baudoin
Synthesis of 1-Indanols and 1-Indanamines by Intramolecular Palladium(0)-Catalyzed C(sp3)-H Arylation: Impact of Conformational Effects [Full Paper]

Synthesis of 1-Indanols and 1-Indanamines by Intramolecular Palladium(0)-Catalyzed C(sp3)-H Arylation: Impact of Conformational Effects

Overcoming strain: A range of valuable 1-indanols and 1-indanamines containing a tertiary C1 atom were synthesized by intramolecular palladium(0)-catalyzed C(sp3)-H arylation (see scheme; PivOK=potassium pivalate). Reactivity and diastereoselectivity differences among the different substrates can be rationalized by conformational analysis.

Chem. Eur. J. 2014, 20, No. 35, 11084-11090

Julia Pedroni, Michele Boghi, Tanguy Saget, Nicolai Cramer
Access to β-Lactams by Enantioselective Palladium(0)-Catalyzed C(sp3)-H Alkylation [Communication]

Access to β-Lactams by Enantioselective Palladium(0)-Catalyzed C(sp3)-H Alkylation

Strain away: Chiral β-lactams are obtained from readily accessible chloroacetamides by an asymmetric palladium(II)-catalyzed C-H functionalization in high yields and excellent enantioselectivities. Important aspects of this transformation are the challenging strain-building C(sp3)-C(sp3) reductive elimination to form the four-membered ring. Ad=adamanyl.

Angew. Chem. Int. Ed. 2014, 53, No. 34, 9064-9067

Yingwei Zhao, Yinjun Xie, Chungu Xia, Hanmin Huang
Palladium-Catalyzed Intramolecular Oxidative C-H Sulfuration of Aryl Thiocarbamates [Communication]

tert-Butyl Nitrite Mediated Regiospecific Nitration of (E)-Azoarenes through Palladium-Catalyzed Directed C-H Activation

Well placed: An efficient protocol for the Pd-catalyzed regiospecific ortho-nitration of (E)-azoarenes has been achieved by using tBuONO as a nitrating agent under atmospheric oxygen. A series of both symmetrical and unsymmetrical azoarenes were nitrated efficiently by this procedure, providing excellent chemo- and regioselectivity and compatibility with a broad array of functional groups.

Chem. Eur. J. 2014, 20, No. 32, 9862-9866

Kedong Yuan, Julien Boixel, Agisilaos Chantzis, Denis Jacquemin , Véronique Guerchais, Henri Doucet
Benzothiophene or Benzofuran Bridges in Diaryl Ethenes: Two-Step Access by Pd-Catalyzed C-H Activation and Theoretical/Experimental Studies on Their Photoreactivity [Full Paper]

Benzothiophene or Benzofuran Bridges in Diaryl Ethenes: Two-Step Access by Pd-Catalyzed C-H Activation and Theoretical/Experimental Studies on Their Photoreactivity

A series of terarylenes incorporating a benzothiophene or a benzofuran as the central ethene unit was synthesized by means of sequential Pd-catalysed C-H activation reactions (see figure). This new methodology allows easy modification of the nature of the pendant heteroarene groups. A study on their photochromic properties revealed that the natures of the heteroarene nature and the central unit drastically modify their photochromic behavior.

Chem. Eur. J. 2014, 20, No. 32, 10073-10083

Exploring Bis(cyclometalated) Ruthenium(II) Complexes as Active Catalyst Precursors: Room-Temperature Alkene–Alkyne Coupling for 1,3-Diene Synthesis

C-H activation: The ruthenium catalyst 1 promoted coupling between acrylic esters and amides with internal alkynes to form 1,3-diene products at room temperature. A proposed catalytic cycle involves C-C bond formation by oxidative cyclization, β-hydride elimination, and C-H bond reductive elimination.

Angew. Chem. Int. Ed. 2014, 53, No. 32, 8437-8440

Dmitry Katayev, Kai F. Pfister, Timo Wendling, Lukas J. Gooßen
Copper-Mediated ortho-Nitration of (Hetero)Arenecarboxylates [Communication]

Copper-Mediated ortho-Nitration of (Hetero)Arenecarboxylates

Mild and selective: In the presence of [CuNO3(PPh3)2], aromatic and heteroaromatic 8-aminoquinolinyl amides undergo selective ortho-C-H nitration under exceptionally mild conditions. A microwave-assisted cleavage of the amide directing group allows regeneration of the carboxylate group within minutes. The carboxylate may be tracelessly removed in situ, or substituted by aryl or alkoxy groups in decarboxylative processes (see scheme; NH2Q=8-aminoquinoline, X=CO2H, H, Ar, OR).

Chem. Eur. J. 2014, 20, No. 32, 9902-9905

Iridium-Catalyzed Regioselective Silylation of Aromatic and Benzylic C-H Bonds Directed by a Secondary Amine

A 'SiN'ch: In the title reaction of benzylamines or anilines, (hydrido)silyl amines are generated in situ which undergo selective silylation at the C-H bond γ to the amino group. The silylation products can be further functionalized through oxidation, halogenation, and cross-coupling reactions. cod=1,5-cyclooctadiene, nbe=norbornene.

Angew. Chem. Int. Ed. 2014, 53, No. 32, 8471-8474

Laurent Djakovitch, François-Xavier Felpin
Direct C sp2-H and C sp3-H Arylation Enabled by Heterogeneous Palladium Catalysts [Minireview]

Direct C sp2-H and C sp3-H Arylation Enabled by Heterogeneous Palladium Catalysts

When palladium meets a support: The functionalization of the C-H bond is the most straightforward approach to create new bonds. Although most studies involve homogeneous transition-metal catalysts, in this Minireview we aim to give a picture of recent advances of direct C-H arylations enabled by heterogeneous Pd catalysts.

ChemCatChem 2014, 6, No. 08, 2175-2187

Jamal Koubachi, Saïd El Kazzouli, Mosto Bousmina, Gérald Guillaumet
Functionalization of Imidazo[1,2-a]pyridines by Means of Metal-Catalyzed Cross-Coupling Reactions [Microreview]

Functionalization of Imidazo[1,2-a]pyridines by Means of Metal-Catalyzed Cross-Coupling Reactions

The latest developments in the field of imidazo[1,2-a]pyridine functionalization by means of cross-coupling reactions such as the Sonogashira, Heck, Negishi, Suzuki–Miyaura, and Stille reactions, as well as by C-arylation, C-alkenylation, carbonylation, and double functionalization, are reviewed and discussed.

Eur. J. Org. Chem. 2014, No. 24, 5119-5138

Facile Access to 1H-Indazoles through Iodobenzene-Catalyzed C–H Amination under Mild, Transition-Metal-Free Conditions

Transition-metal- and halogen-free synthesis of N-aryl-substituted 1H-indazole and derivatives is accomplished on the basis of the iodobenzene-catalyzed intramolecular C–H amination of hydrazones in the presence of Oxone in trifluoroacetic acid at –10 °C. The 1H-indazole derivatives are obtained in moderate to good yields (up to 90 %).

Eur. J. Org. Chem. 2014, No. 22, 4720-4723

Ligands Control Reactivity and Selectivity in Palladium-Catalyzed Functionalization of Unactivated C sp3-H Bonds

Ligands at the wheel: The pivotal role of ligands for the palladium-catalyzed functionalization of remote C sp3-H bonds has been demonstrated. The presence of the ligand enhances the reactivity of the inert C sp3-H bond and controls the selectivity of the process. DG=Directing group, FG=functional group.

ChemCatChem 2014, 6, No. 08, 2188-2190

Hamad H. Al Mamari, Emelyne Diers, Lutz Ackermann
Triazole-Assisted Ruthenium-Catalyzed C-H Arylation of Aromatic Amides [Full Paper]

Triazole-Assisted Ruthenium-Catalyzed C-H Arylation of Aromatic Amides

Assisting activation: Ruthenium(II)-catalyzed C-H arylations of (hetero)arenes and alkenes have been achieved with aryl halides through removable bidentate auxiliaries derived from modular 1,2,3-triazoles (see scheme; TAM=triazolyldimethylmethyl).

Chem. Eur. J. 2014, 20, No. 31, 9739-9743

Modular Synthesis of Phenanthro[9,10-c]thiophenes by a Sequence of C-H Activation, Suzuki Cross-Coupling and Photocyclization Reactions

Three C-C bond formation reactions are successively coupled in a convergent synthesis of phenanthro[9,10-c]thiophenes A. The key reaction is an unprecedented photocyclization of precursors B, which proceeds cleanly at λ=254 nm (60–82 % yield). Diarylthiophenes B are conveniently assembled employing a sequence of oxidative and regular Suzuki cross-coupling reactions.

Chem. Eur. J. 2014, 20, No. 31, 9725-9732

Direct Functionalization with Complete and Switchable Positional Control: Free Phenol as a Role Model

PhenAll: Recent breakthroughs in site-selective and direct functionalization of free phenols by transition-metal-catalyzed C-O or C-H bond activation are highlighted here as role models for the complete and switchable positional control of transformations of important core structures.

Angew. Chem. Int. Ed. 2014, 53, No. 30, 7710-7712

Jaika Dörfler, Till Preuß, Alexandra Schischko, Marc Schmidtmann, Sven Doye
A 2,6-Bis(phenylamino)pyridinato Titanium Catalyst for the Highly Regioselective Hydroaminoalkylation of Styrenes and 1,3-Butadienes [Communication]

A 2,6-Bis(phenylamino)pyridinato Titanium Catalyst for the Highly Regioselective Hydroaminoalkylation of Styrenes and 1,3-Butadienes

Linear progress: A new Ti complex with 2,6-bis(phenylamino)pyridinato ligands catalyzes highly regioselective hydroaminoalkylation reactions of styrenes. The process that directly gives access to the corresponding linear hydroaminoalkylation products offers a new and flexible synthetic approach towards pharmaceutically important 3-arylpropylamines. It is also possible to convert (E)-1-phenyl-1,3-butadienes into the corresponding linear products.

Angew. Chem. Int. Ed. 2014, 53, No. 30, 7918-7922

Silylative Coupling versus Metathesis—Efficient Methods for the Synthesis of Difunctionalized Double-Decker Silsesquioxane Derivatives

Divinyl-substituted double-decker silsesquioxanes (DDSQ-2SiVi) have been functionalized by a highly effective silylative coupling and/or metathesis with olefins. Both reactions proceed highly stereoselectively and lead to nearly quantitative formation of E isomers. Preliminary studies on the silylative coupling of DDSQ-2SiVi with 1,4-divinylbenzene resulted in a stereoregular cooligomer containing double-decker (silsesquioxyl-silylene)-vinylene-phenylene units.

Chem. Eur. J. 2014, 20, No. 30, 9387-9393

Yan Li, Yun Wu, Guang-Shui Li, Xi-Sheng Wang
Palladium-Catalyzed C-F Bond Formation via Directed C-H Activation [Review]

Christoph Kornhaaß, Christian Kuper, Lutz Ackermann
Ferrocenylalkynes for Ruthenium-Catalyzed Isohypsic C-H/N-O Bond Functionalizations [Update]

Suman De Sarkar, Weiping Liu, Sergei I. Kozhushkov, Lutz Ackermann
Weakly Coordinating Directing Groups for Ruthenium(II)- Catalyzed C-H Activation [Review]

Zhao-Lei Yan, Wen-Liang Chen, Ya-Ru Gao, Shuai Mao, Yan-Lei Zhang, Yong-Qiang Wang
Palladium-Catalyzed Intermolecular C-2 Alkenylation of Indoles Using Oxygen as the Oxidant [Update]

José Luis García Ruano, José Alemán, Alejandro Parra, Leyre Marzo
Sulfonyl Acetylenes as Alkynylating Reagents Under Radical or Anionic Conditions [Microreview]

Sulfonyl Acetylenes as Alkynylating Reagents Under Radical or Anionic Conditions

We summarize a powerful methodology for the alkynylation of C(sp3), C(sp2), and C(sp) carbon atoms, as well as some heteroatoms, with alkynylsulfones. It is based on the fact that β-substituted sulfonylacetylenes undergo unexpected anti-Michael addition of organolithiums and radical species, giving intermediates that evolve into alkynyl derivatives in situ by elimination of the anion or radical TolSO2.

Eur. J. Org. Chem. 2014, No. 08, 1577-1588

Philipp J. Gritsch, Christian Leitner, Magnus Pfaffenbach, Tanja Gaich
The Witkop Cyclization: A Photoinduced C-H Activation of the Indole System [Minireview]

The Witkop Cyclization: A Photoinduced C-H Activation of the Indole System

To wit: The title reaction resembles a photoinduced electron-transfer process, and allows the direct formation of medium-sized lactams by C-H activation of the indole nucleus. Therefore it is a versatile tool for the construction of polycyclic indole alkaloid scaffolds.

Angew. Chem. Int. Ed. 2014, 53, No. 05, 1208-1217

Towards Ideal Synthesis: Alkenylation of Aryl C-H Bonds by a Fujiwara–Moritani Reaction

Chemical power tools: The Fujiwara–Moritani reaction is the palladium-catalyzed coupling reaction of a simple aryl C-H bond with an alkenyl C-H bond to form a new C-C bond (see scheme). This Minireview focuses on the advances in the past five years related to the activation of various aryl C-H bonds in this coupling reaction.

Chem. Eur. J. 2014, 20, No. 03, 634-642

The Cross-Dehydrogenative Coupling of Csp3-H Bonds: A Versatile Strategy for C-C Bond Formations

Waste not, want not: The title CDC reactions have emerged as versatile tools for selective and waste-minimized C-C bond formations. They rely on the direct coupling of two different C-H bonds under oxidative conditions. This Review focuses on the recent progress in cross-dehydrogenative Csp3-C formation and provides a comprehensive overview on existing procedures and employed methodologies.

Angew. Chem. Int. Ed. 2014, 53, No. 01, 74-100

New Site-Selective Organoradical Based on Hypervalent Iodine Reagent for Controlled Alkane sp3 C-H Oxidations

Large Iodine: The site-selective oxidation of unactivated secondary sp3 C-H bonds was accomplished by using a newly defined reactive hypervalent iodine(III) radical in the presence of tert-butyl hydroperoxide (see scheme). Recent studies on hypervalent iodine radicals have significantly contributed to the further development and design of organic molecules in radical oxidation chemistry.

ChemCatChem 2014, 6, No. 01, 76-78

Yinuo Wu, Jun Wang, Fei Mao, Fuk Yee Kwong
Palladium-Catalyzed Cross-Dehydrogenative Functionalization of C(sp2)-H Bonds [Focus Review]

Palladium-Catalyzed Cross-Dehydrogenative Functionalization of C(sp2)-H Bonds

Caught in the cross-fire: This Review highlights the recent developments in catalytic cross-dehydrogenative coupling (CDC) reactions, which join together two aromatic C-H fragments through a palladium-catalyzed dehydrogenative pathway.

Chem. Asian J. 2014, 9, No. 01, 26-47

© Wiley-VCH 2013.