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
[Rh(III)Cp*]-catalyzed directed C-H bromination and iodination reaction of 2-aryl isoquinolines/pyridines is highly efficient to provide atropisomeric biaryl compounds. Among several reported C-H bond halogenation methods, the combination of [Rh(III)Cp*Cl2]Cl2/AgSbF6, N-halosuccinimide, and pivalic acid in 1,2-dichloroethane is found to be the only effective catalytic system to provide atropisomeric 2'-halogenated 2-aryl isoquinolines/pyridines.
Kiseong Kim, Jaeyong Hyun, Jin Kim, Hyunwoo Kim
Asian J. Org. Chem., June 27, 2016, DOI: 10.1002/ajoc.201600259. Read article
Formel notice: Recent years have witnessed an upsurge in annulations based on C−H activation that can be formally considered as cycloaddition processes. These transformations are particularly appealing from a synthetic perspective because they allow the conversion of readily available substrates into highly valuable cyclic products in a rapid and sustainable manner.
Moisés Gulías, José Luis Mascareñas
Angew. Chem. Int. Ed., June 22, 2016, DOI: 10.1002/anie.201511567. Read article
Lights on elementary revelations: Mechanistic details of methane-to-syngas formation and activation of methane on Mn-doped ceria zirconia porous thin films are explored by means of a molecular-beam investigation. Competition and cooperation among different elementary reactions under complementary conditions are found.
Anjani Dubey, Sadhu K. Kolekar, Chinnakonda S. Gopinath
ChemCatChem, June 21, 2016, DOI: 10.1002/cctc.201600365. Read article
U can do it: The uranyl cation (UO22+) is able to effect the catalytic fluorination of unactivated C(sp3)−H bonds under visible-light irradiation. Uranyl nitrate is highlighted as a convenient molecular C−H abstraction catalyst, which exhibits selectivity that is distinct from previously reported catalytic systems. NFSI: N-fluorobenzenesulfonimide.
Julian G. West, T. Aaron Bedell, Erik J. Sorensen
Angew. Chem. Int. Ed., June 20, 2016, DOI: 10.1002/anie.201603149. Read article
Alkynes of fun: Fe3O4 nanoparticles separately supported on charcoal, graphene, and SBA-15 are prepared by solid-state grinding and subsequent thermal treatment. The Fe3O4 nanoparticles supported on activated charcoal exhibit high catalytic activity and furnish good yields of alkynyl selenide products in the cross-coupling reactions of diphenyl diselenide with alkynes through C−H and Se−Se bond activation under ecofriendly conditions.
Balaji Mohan, Ji Chan Park, Kang Hyun Park
ChemCatChem, June 17, 2016, DOI: 10.1002/cctc.201600280. Read article
Zechao Wang, Yahui Li, Fengxiang Zhu, Xiao-Feng Wu
Adv. Synth. Catal., June 15, 2016, DOI: 10.1002/adsc.201600395. Read article.
Over the past few years, substantial progress has been achieved in the development of nitroso derivatives. Cyclization reactions of nitroso compounds, especially the hetero Diels-Alder-type reaction, have drawn much interest from organic chemists, because of their regioselective, enantioselective and highly efficient advantages. In addition, the N-nitroso moiety can also be employed as powerful and transformable directing group in specific C-H direct functionalization reactions. Herein, we summarized the versatile applications of nitroso compounds as useful building blocks in the selective synthesis of diverse molecules in recent years.
Zhiyuan Chen, Jiapian Huang, Jianjun Yuan, Yiyuan Peng
Asian J. Org. Chem., June 15, 2016, DOI: 10.1002/ajoc.201600242. Read article
An A3 Couple: A series of novel (4S,8aS)-3,4-diphenyl-6,7,8,8a-tetrahydro-4H-isoxazolo[3,4-a]pyrrolizines have been synthesized through a CuII acetylacetonate-catalyzed solvent-free multicomponent coupling reaction (MCR), followed by 1,3-dipolar cycloaddition. This method demonstrates high structural diversity and generates desired products in satisfactory yields and diastereoselectivities.
Shakil N. Afraj, Cut Nuzlia, Chinpiao Chen, Gene-Hsian Lee
Asian J. Org. Chem., June 09, 2016, DOI: 10.1002/ajoc.201600223. Read article
Ye-Xing Lao, Shang-Shi Zhang, Xu-Ge Liu, Chun-Yong Jiang, Jia-Qiang Wu, Qingjiang Li, Zhi-Shu Huang, Honggen Wang
Adv. Synth. Catal., June 7, 2016, DOI: 10.1002/adsc.201600194. Read article.
Bhuttu Khan, Ruchir Kant, Dipankar Koley
Adv. Synth. Catal., June 7, 2016, DOI: 10.1002/adsc.201600177. Read article.
Directing hydroarylation: RhIII-catalyzed hydroarylation of internal alkynes through C−H bond activation is described by using N,N-dimethylaminocarbonyl as a directing group. This protocol enables exceptional functionality compatibility because of the mild reaction conditions employed and provides a highly efficient route for the introduction of olefins. By taking advantage of the difference of innate binding abilities of the assisting group, consecutive introduction of two different types of alkene moiety was readily realized.
Cheng-Qiang Wang, Chao Feng, Teck-Peng Loh
Asian J. Org. Chem., June 03, 2016, DOI: 10.1002/ajoc.201600144. Read article
Julian Wippich, Nadina Truchan, Thorsten Bach
Adv. Synth. Catal., June 2, 2016, DOI: 10.1002/adsc.201600410. Read article.
Anju Modi, Wajid Ali, Bhisma K. Patel
Adv. Synth. Catal., June 2, 2016, DOI: 10.1002/adsc.201600067. Read article.
Chelate-assisted C(sp3)−H bond activation: The dehydrogenative silylation of 2-alkyloxazolines with 1,1,1,3,5,5,5-heptamethyltrisiloxane took place site-selectively at methyl C(sp3)−H bonds located γ to the nitrogen atom of the oxazolyl groups.
Kazumasa Kon, Hiroyuki Suzuki, Kosuke Takada, Yoshihito Kohari, Takeshi Namikoshi, Shinji Watanabe, Miki Murata
ChemCatChem, June 02, 2016, DOI: 10.1002/cctc.201600312. Read article
Prakash Ranjan Mohanta, Arghya Banerjee, Sourav Kumar Santra, Ahalya Behera, Bhisma K. Patel
Adv. Synth. Catal., May 31, 2016, DOI: 10.1002/adsc.201600258. Read article.
Quick to react: A procedure for the oxidative synthesis of β-hydroxysulfides is reported, in which thiophenols or diaryl disulfides are reacted with tert-butyl hydroperoxide (TBHP). In the presence of zinc iodide or potassium iodide, with TBHP as the oxidant and pre-reactant, thiophenols and diaryl disulfides react with the methyl group of tBuOH smoothly and selectivity to give the corresponding 2-methyl-1-(arylthio)propan-2-ols as the terminal products in moderate to good yields.
Jian-Bo Feng, Xiao-Feng Wu
ChemistryOpen, May 17, 2016, DOI: 10.1002/open.201600023. Read article
Xiaoxu Yang, Xiqing Jin, Congyang Wang
Adv. Synth. Catal., May 9, 2016, DOI: 10.1002/adsc.201600128. Read article.
All positions in carbohydrates have been functionalized through C–H bond cleavage, hence paving the way for easy access to complex modified sugars or natural products. This review presents the methods available for C–H functionalization in carbohydrate chemistry and gives an overview position-by-position.
Tobias Gylling Frihed, Mikael Bols, Christian Marcus Pedersen
Eur. J. Org. Chem., March 21, 2016, DOI: 10.1002/ejoc.201600121. Read article.
This microreview presents work surrounding the development and study of Tp-supported platinum group metal complexes for stoichiometric and catalytic C–H bond activation. From κ2- and κ3-coordination modes to increased sterics to electronic parameters, Tp and related ligands have played an important role in the observed reactivity of Ru, Rh and Pt-mediated C–H bond activation reactions.
Bradley A. McKeown, John P. Lee, Jiajun Mei, Thomas R. Cundari, T. Brent Gunnoe
Eur. J. Inorg. Chem., February 12, 2016, DOI: 10.1002/ejic.201501470. Read article.
The IrIII complex [TpMe2Ir(C6H5)2(N2)] [TpMe2 = hydridotris(3,5-dimethylpyrazolyl)borate] reacts with different olefins to yield organometallic compounds that derive from allylic C–H activations in processes that also generate organic coupling products that involve the vinylic positions of the olefin.
Crispín Cristóbal, Laura L. Santos, Rubén Gutiérrez-González, Eleuterio Alvarez, Margarita Paneque, Manuel L. Poveda
Eur. J. Inorg. Chem., January 19, 2016, DOI: 10.1002/ejic.201501253. Read article.
Two in one: The Ir–imine-functionalized protic N-heterocyclic carbene (pNHC) complex was obtained through a chelate-assisted C2-H bond activation in the cationic Nimidazole-Ir complex. New homo- and heterodinuclear complexes could be prepared by in situ deprotonation of either the neutral Nimidazole-Ir complex or the Ir pNHC complex followed by addition of metal precursors (see scheme).
Fan He, Marcel Wesolek, Andreas A. Danopoulos, Pierre Braunstein
Chem. Eur. J., January 15, 2016, DOI: 10.1002/chem.201504030. Read article.
Ligands of tomorrow: Chiral spirocyclic sultams are rapidly assembled in a [3+2] annulation from N-sulfonyl ketimines and alkynes. The transformation is catalyzed by rhodium complexes equipped with the atropchiral biaryl Cpx ligand, and provides the sultams in excellent yields and high enantioselectivities.
Manh V. Pham, Nicolai Cramer
Chem. Eur. J., January 11, 2016, DOI: 10.1002/chem.201504998. Read article.
Chains linked: Through the interplay of high-resolution scanning tunneling microscopy imaging and density functional theory calculations, the stepwise homocoupling of alkyl chains on Cu(110) is demonstrated, proceeding from the intact chain, via the dehydrogenative intermediates, to the final coupling products.
Liangliang Cai, Qiang Sun, Chi Zhang, Yuanqi Ding, Wei Xu
Chem. Eur. J., January 8, 2016, DOI: 10.1002/chem.201504152. Read article.
Access the inaccessible: A copper-catalyzed 8-amide chelation-induced remote C-H amination of quinolines has been developed (see scheme). This direct amination with readily available azodicarboxylates proceeded with perfect C5-regioselectivity offering amino-substituted 8-aminoquinolines in high yields (up to 96 %).
Harekrishna Sahoo, Mallu Kesava Reddy, Isai Ramakrishna, Mahiuddin Baidya
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201504207. Read article.
Origin of the activation: The inner surface structures of the pore wall in mesoporous α-Fe2O3 are mainly comprised of turbostratic ribbons and K crystal faces. They show excellent catalytic performance for methane activation, during which the C-H bonds are converted into C-O bonds in an O2 atmosphere at 140 °C (see figure).
Bing Dong, Zhen Han, Yongbo Zhang, Youyi Yu, Aiguo Kong, Yongkui Shan
Chem. Eur. J., January 7, 2016, DOI: 10.1002/chem.201503183. Read article.
A blockbuster catalyst: Well-defined ruthenium(II) phosphinous acid (PA) complexes were identified as powerful catalysts for highly selective C-H arylations with ample scope, which enabled low catalyst loadings and gave step-economical access to blockbuster drugs. Mechanistic studies were supportive of a PA-assisted C-H activation.
Daniel Zell, Svenja Warratz, Dmitri Gelman, Simon J. Garden, Lutz Ackermann
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504851. Read article.
Alkynes on a gold Tr(i)p! Various peptides and one model protein were functionalized with ethynyl moieties at their tryptophan residues using Waser’s reagent, TIPS-EBX, under gold(I) catalysis (see scheme; TIPS=triisopropylsilyl). The reaction proceeded in a regio- and chemoselective manner leading to C2 substitution at the tryptophan residues only. Subsequently, the terminal alkyne was used to label one of the model peptides with a fluorophore by means of copper-catalyzed click chemistry.
Morten Borre Hansen, František Hubálek, Troels Skrydstrup, Thomas Hoeg-Jensen
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504462. Read article.
Rhoad to alkaloids! A Rh-catalyzed intramolecular C-H bond activation/annulation of aldehydes and alkyne–amines provides a novel efficient method for the synthesis of various protoberberine salts and natural products in high yield under mild reaction conditions.
Jayachandran Jayakumar, Chien-Hong Cheng
Chem. Eur. J., December 22, 2015, DOI: 10.1002/chem.201504378. Read article.
In two shakes: Oxidative annulation by double C-H activation/alkyne insertion reaction was achieved by a nickel/NHC system. A Ni0/NiII catalytic cycle is proposed as the main catalytic cycle. The alkyne plays a double role as a two-component coupling partner and as a hydrogen acceptor.
Luis C. Misal Castro, Atsushi Obata, Yoshinori Aihara, Naoto Chatani
Chem. Eur. J., December 21, 2015, DOI: 10.1002/chem.201504596. Read article.
Influential solvent: Efficient access to atropo-enantioenriched biaryl moieties through asymmetric direct C-H activation, by using enantiopure sulfoxide as both the directing group and chiral auxiliary, is reported (see scheme). The key role of 1,1,1,3,3,3-hexafluoropropanol (HFIP) solvent is investigated.
Quentin Dherbassy, Geoffrey Schwertz, Matthieu Chessé, Chinmoy Kumar Hazra, Joanna Wencel-Delord, Françoise Colobert
Chem. Eur. J., December 18, 2015, DOI: 10.1002/chem.201503650. Read article.
The crucial role of gold in the transformation of ethane to ethene and dihydrogen is observed in the reaction between C2H6 and Au2VO3+ clusters with closed-shell electronic structures. The first C-H activation is initiated by gold rather than an oxygen species. The Au-Au dimer formed during the reactions plays important roles in converting ethane into ethene and making dihydrogen energetically more favorable.
Ya-Ke Li, Zi-Yu Li, Yan-Xia Zhao, Qing-Yu Liu, Jing-Heng Meng, Sheng-Gui He
Chem. Eur. J., December 17, 2015, DOI: 10.1002/chem.201503676. Read article.
Three is a magic number: On treatment of triazoles with [Rh2(C7H15CO2)4], the rhodium catalyst plays three roles, denitrogenation, C-H bond activation, and stereoselective cyclization, providing a new method for heterocycle synthesis. Intramolecular C-H bond insertion takes place at the benzylic position to give pyrrolidines and related heterocycles in good yields.
Masato Senoo, Ayana Furukawa, Takeshi Hata, Hirokazu Urabe
Chem. Eur. J., December 14, 2015, DOI: 10.1002/chem.201503823. Read article.
DDAism: Dehydrogenative cycloadditions have attracted significant attention in synthetic chemistry. This Minireview highlights the recent efforts towards the development of dehydro or dehydrogenative Diels–Alder reactions to construct diverse aromatic compounds by a concerted pathway or a stepwise process.
Wenbo Li, Liejin Zhou, Junliang Zhang
Chem. Eur. J., November 24, 2015, DOI: 10.1002/chem.201503571. Read article.
A directed heterogeneous C-H activation/halogenation reaction catalyzed by readily synthesized Pd@MOF nanocatalysts was developed (see scheme). The heterogeneous Pd catalysts used were a novel and environmentally benign Fe-based metal–organic framework (MOF) (Pd@MIL-88B-NH2(Fe)) and the previously developed Pd@MIL-101-NH2(Cr). Very high conversions and selectivities were achieved under very mild reaction conditions and in short reaction times.
Vlad Pascanu, Fabian Carson, Marta Vico Solano, Jie Su, Xiaodong Zou, Magnus J. Johansson, Belén Martín-Matute
Chem. Eur. J., October 20, 2015, DOI: 10.1002/chem.201502918. Read article.