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
Qiang Wu, Lanlan Wang, Rizhe Jin, Chuanqing Kang, Zheng Bian, Zhijun Du, Xiaoye Ma, Haiquan Guo, Lianxun Gao
Eur. J. Org. Chem., October 18, 2016, DOI: 10.1002/ejoc.201600955. Read article
From simple to complex: A palladium-catalyzed cascade Heck carbopalladation/C−H activation/aryne insertion provides easy access to spirobiaryls. The process tales advantage of several aspects of Pd chemistry, i.e., intra- and intermolecular carbopalladation of unsaturated species, C−H activation and C−C coupling processes.
Marta Pérez-Gómez, José-Antonio García-López
Angew. Chem. Int. Ed., October 14, 2016, DOI: 10.1002/anie.201607976. Read article
Breaking the resistance: 8-Aminoquinoline has emerged as one of the most powerful bidentate-directing groups in history of C−H activation within the last decade. However, cleavage of its robust amide bond has proved to be challenging in several cases. To overcome this limitation, a simple and mild oxidative deprotection protocol is reported that allows subsequent cleavage in a simple one-pot fashion to rapidly access carboxylic acids or amides as final products.
Martin Berger, Rajan Chauhan, Catarina A. B. Rodrigues, Nuno Maulide
Chem. Eur. J., October 13, 2016, DOI: 10.1002/chem.201604344. Read article
Palladium-catalyzed C–H arylations of benzamides were accomplished with the assistance of removable triazole amines (TAMs). This operationally simple protocol proceeded under silver-free reaction conditions and is characterized by having an ample substrate scope and broad functional group tolerance.
Darko Santrač, Stefano Cella, Wei Wang, Lutz Ackermann
Eur. J. Org. Chem., October 11, 2016, DOI: 10.1002/ejoc.201601045. Read article
Grzegorz Filipczyk, Steve W. Lehrich, Alexander Hildebrandt, Tobias Rüffer, Dieter Schaarschmidt, Marcus Korb, Heinrich Lang
Eur. J. Inorg. Chem., October 05, 2016, DOI: 10.1002/ejic.201600848. Read article
Cobalt coupling double-crossed: Efficient and general cobalt(III)-catalyzed intramolecular cross-dehydrogenative C−H/N−H coupling of ortho-alkenylanilines have been developed utilizing molecular oxygen as terminal oxidant for the synthesis of diverse indole derivatives in good to excellent yields. Successful extension of the method was demonstrated through intramolecular cross-dehydrogenative C−H/O−H coupling of ortho-alkenylphenols for the synthesis of benzofurans.
Jayanta Ghorai, Angula Chandra Shekar Reddy, Pazhamalai Anbarasan
Chem. Eur. J., September 30, 2016, DOI: 10.1002/chem.201604111. Read article
Intermolecular amination of unactivated C(sp3)−H bonds by cyclic alkylamines mediated by Cu(OAc)2/O2 has been reported. This method avoids the use of benzoyloxyamines as the aminating reagent. A variety of unnatural β2, 2-amino acid analogues are synthesized by this simple and efficient procedure (see scheme).
Quan Gou, Yu-Wen Yang, Zi-Ning Liu, Jun Qin
Chem. Eur. J., September 29, 2016, DOI: 10.1002/chem.201603370. Read article
R-u there, aniline? Water-soluble arene–ruthenium complexes coordinated with aniline-based ligands are successfully employed in the C−H bond activation and arylation of 2-phenylpyridine with a wide range of (hetero)aryl halides to afford the corresponding ortho-monoarylated products as major products in moderate to good yields (up to 73 %). The electronic and steric properties of the coordinating aniline-based ligands have a significant effect on catalytic activity.
Chinky Binnani, Deepika Tyagi, Rohit K. Rai, Shaikh M. Mobin, Sanjay K. Singh
Chem. Asian J., September 29, 2016, DOI: 10.1002/asia.201600954. Read article
Good to Si you: A general and practical PdII-catalyzed intermolecular silylation of primary and secondary C−H bonds of α-amino acids and simple aliphatic acids is reported. This method provides divergent and stereoselective access to a variety of optical pure β-silyl-α-amino acids. Furthermore, the late-stage functionalization of biological small molecules such as (−)-santonin and β-cholic acid is demonstrated.
Yue-Jin Liu, Yan-Hua Liu, Zhuo-Zhuo Zhang, Sheng-Yi Yan, Kai Chen, Bing-Feng Shi
Angew. Chem. Int. Ed., September 28, 2016, DOI: 10.1002/anie.201607766. Read article
The Au-catalyzed reaction of ferrocene with propargylic esters provides ferrocene derivatives featuring a functionalized vinyl moiety through initial 1,2-acyloxy rearrangement with generation of a gold carbene intermediate and subsequent electrophilic aromatic substitution. This method demonstrates the potential of carbene intermediates in the C–H bond functionalization of ferrocene.
Enol López, Tatiana Suárez, Alfredo Ballesteros, Luis A. López
Eur. J. Inorg. Chem., August 29, 2016, DOI: 10.1002/ejic.201600836. Read article
In this account we summarize and discuss synthetic solutions for the realization of palladium catalyzed, ortho-directed C-H functionalization of aniline derivatives under mild reaction conditions for the construction of new carbon-carbon and carbon-oxygen bonds.
Orsolya Tischler, Balázs Tóth, Zoltán Novák
The Chemical Record, August 09, 2016, DOI: 10.1002/tcr.201600059. Read article