10273-89-9Relevant articles and documents
Manganese-catalyzed directed methylation of C(sp2)-H bonds at 25 °C with high catalytic turnover
Sato, Takenari,Yoshida, Takumi,Al Mamari, Hamad H.,Ilies, Laurean,Nakamura, Eiichi
, p. 5458 - 5461 (2017)
We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl2· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 103, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.
Cyclometallated ruthenium catalyst enables late-stage directed arylation of pharmaceuticals
Simonetti, Marco,Cannas, Diego M.,Just-Baringo, Xavier,Vitorica-Yrezabal, I?igo J.,Larrosa, Igor
, p. 724 - 731 (2018)
Biaryls are ubiquitous core structures in drugs, agrochemicals and organic materials that have profoundly improved many aspects of our society. Although traditional cross-couplings have made practical the synthesis of many biaryls, C-H arylation represents a more attractive and cost-effective strategy for building these structural motifs. Furthermore, the ability to install biaryl units in complex molecules via late-stage C-H arylation would allow access to valuable structural diversity, novel chemical space and intellectual property in only one step. However, known C-H arylation protocols are not suitable for substrates decorated with polar and delicate functionalities, which are commonly found in molecules that possess biological activity. Here we introduce a class of ruthenium catalysts that display a unique efficacy towards late-stage arylation of heavily functionalized substrates. The design and development of this class of catalysts was enabled by a mechanistic breakthrough on the Ru(ii)-catalysed C-H arylation of N-chelating substrates with aryl (pseudo)halides, which has remained poorly understood for nearly two decades.
Biphenylene-Substituted Ruthenocenylphosphine for Suzuki-Miyaura Coupling of Aryl Chlorides
Hoshi, Takashi,Nakazawa, Taichi,Saitoh, Ippei,Mori, Ayako,Suzuki, Toshio,Sakai, Jun-Ichi,Hagiwara, Hisahiro
, p. 2063 - 2066 (2008)
High activity in the palladium-catalyzed Suzuki-Miyaura reactions of aryl chlorides with arylboronic acids was furnished using biphenylene-substituted di-tert-butylruthenocenylphosphine (R-Phos) as a supporting ligand. Substrate combinations even for the construction of highly hindered tetra-ortho- substituted biaryls can be achieved in good to excellent yields with low catalyst loadings in short reaction times.
Aromatic C-H Methylation and Other Functionalizations via the Rh(III)-Catalyzed Migratory Insertion of Bis(phenylsulfonyl)carbene and Subsequent Transformations
Chen, Lei,Peng, Rui-Jun,Zhang, Xue-Jing,Yan, Ming,Chan, Albert S. C.
, p. 10177 - 10189 (2021)
The Rh(III)-catalyzed migratory insertion of bis(phenylsulfonyl)carbene into aromatic C-H bonds has been developed. A variety of bis(phenylsulfonyl)methyl derivatives were prepared with good yields under mild conditions. The methylated products were readily obtained after reductive desulfonylation. Furthermore, the diverse transformations of bis(phenylsulfonyl)methyl to trideuteriomethyl, aldehyde, and other functional groups were demonstrated.
Catalytic meta-selective C-H functionalization to construct quaternary carbon centres
Paterson, Andrew J.,St John-Campbell, Sahra,Mahon, Mary F.,Press, Neil J.,Frost, Christopher G.
, p. 12807 - 12810 (2015)
A catalytic meta-selective C-H functionalization of 2-phenylpyridines using a range of tertiary halides is described. The protocol is simple to perform and uses commercially available reagents to construct challenging quaternary carbon centres in a regioselective manner. Preliminary studies suggest the C-H functionalization proceeds through a radical process directed via a remote σ-activation.
Nickel-Catalyzed Cross-Coupling Reaction of Aryl Sulfoxides with Arylzinc Reagents: When the Leaving Group is an Oxidant
Yamamoto, Keita,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki
, p. 7623 - 7628 (2017)
Nickel-catalyzed Negishi-type cross-coupling of aryl methyl sulfoxides with arylzinc reagents has been developed. By consuming the catalyst-oxidizing methanesulfenate anion through oxidative homocoupling of the arylzinc reagent, smooth catalyst turnover c
Cucurbit[8]uril recognition of rapidly interconverting diastereomers
Joseph, Roymon,Masson, Eric
, p. 632 - 641 (2014)
The diastereoselectivity of Cucurbit[8]uril (CB[8]) binding was probed towards a series of rapidly interconverting diastereomers containing a Caryl-Caryl chiral axis and at least one other stereocenter. Relative binding affinities of up to 4.9 were determined when CB[8] interacted with ortho, meta, ortho′-substituted biphenyls bearing a chiral dialkylsulfonium substituent at their meta-position. Diastereoselectivities of up to 2.4-fold were obtained for ortho′-substituted 2-phenylpyridinium derivatives that bear a chiral myrtenyl N-substituent prone to CB[8] binding.
Palladium-catalyzed C-H alkylation of 2-phenylpyridines with alkyl iodides
Wang, Xiaoling,Ji, Xiaoming,Shao, Changdong,Zhang, Yu,Zhang, Yanghui
, p. 5616 - 5624 (2017)
Palladium-catalyzed C-H alkylation reaction of 2-phenylpyridines with alkyl iodides has been successfully developed. The palladacycles obtained from 2-phenylpyridines should act as the key intermediates in the alkylation reaction.
Palladium (II) Complexes Containing 2-Phenylpyridine Derivatives: Synthesis, Molecular Structures, and Catalytic Activity for Suzuki–Miyaura Cross-Coupling Reactions
Adamson, A.,Alhaddad, M. R.,Arshad, M. N.,Asiri, A. M.,Budiman, Y. P.,Mkhalid, I.,Muhammad, R.
, p. 466 - 475 (2020)
The preparation and characterization of a series of new 2-phenylpyridine derivative ligands consisting of 2-(R) pyridine (R = mesityl (L1), 2,6-dimethylphenyl (L2), o-tolyl (L3), m-tolyl (L4), p-tolyl (L5), o-methoxyphenyl (L6), and p-methoxyphenyl (L7)) and their Pd complexes [PdCl2L2] (L1–L7) is investigated using a combination of X-ray diffraction spectroscopy, GC-MS, and NMR. The crystal structures show that the Pd complexes adopt a square planar geometry, and the monodentate ligand is coordinated through the N donor of the pyridine ring to the Pd atom. The catalytic activities of the synthesized complexes are investigated. The square planar Pd complex trans-[(2-mesitylpy)2PdCl2)] shows a high efficiency in promoting Suzuki-Miyaura cross coupling in an aqueous solvent under aerobic conditions.
Cobalt(iii) complexes bearing bidentate, tridentate, and tetradentate N-heterocyclic carbenes: Synthesis, X-ray structures and catalytic activities
Xi, Zhenxing,Liu, Bin,Lu, Chunxin,Chen, Wanzhi
, p. 7008 - 7014 (2009)
Cobalt(iii) complexes, [CoCl2(L1)2](PF6) (1, L1 = N-methyl-N-(2-pyrimidinyl)imidazolylidene), [CoCl(L2) 2](PF6)2 (2, L2 = N-picolyl-(2-pyrimidinyl) imidazolylidene), [Co(L3)2](PF6)3 (3, L3 = bis(N-2-pyrimidylimidazolylidenyl)methane) and [CoCl2(L3)](PF 6) (4) have been prepared from the corresponding pyrimidine functionalized imidazolium salts [HL1](PF6), [HL2](PF6), and [H2L3](PF6)2via in situ generated silver carbene complexes under mild conditions. These cobalt complexes were characterized by 1H and 13C NMR spectroscopy and X-ray diffraction analysis. The cobalt complexes have been found to be good catalyst precursors for Kumada-Corriu cross-coupling reactions of aryl halides and Grignard reagents at room temperature. Complex 1 is more active under the mild conditions.
