- Copper acetoacetonate [Cu(acac)2]/BINAP-promoted Csp 3-N bond formation via reductive coupling of N-tosylhydrazones with anilines
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We report the the copper(II) acetoacetonate [Cu(acac)2]/BINAP- catalyzed synthesis of arylamines from N-tosylhydrazones and anilines. A fine tuning of the reaction conditions was required to accomplish the cross-coupling successfully, including the ligands effect and the addition of small amounts of water. The characteristic feature of this protocol is its functional group compatibility and its chemoselectivity when various aminophenol derivatives were used. Taking into consideration the interest for this copper-reductive coupling in which no stoichiometric metal hydride reagent is employed, this can be considered as an alternative to the conventional reductive amination.
- Aziz, Jessy,Brion, Jean-Daniel,Hamze, Abdallah,Alami, Mouad
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- Pd-Catalyzed Coupling of Thioamides with N-Tosylhydrazones/Trapping by Esters Cascade Reaction
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N,N-Disubstituted thioamides coupled with N-tosylhydrazones under Pd(TFA)2/tBuXPhos catalyst and NaOtBu, and the intermediates from palladium carbene migratory insertion containing β-hydrogen were trapped by intramolecular esters activated by BF3·Et2O ins
- Cai, Zhongliang,Yao, Zhi,Jiang, Liqin
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supporting information
p. 311 - 316
(2021/01/26)
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- Aryl-Diadamantyl Phosphine Ligands in Palladium-Catalyzed Cross-Coupling Reactions: Synthesis, Structural Analysis, and Application
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Synthesis, temperature-dependent NMR structure investigation and utilization of a new, stable and easily accessible aryl-diadamantylphosphine ligand family is reported. The bulky and electron-rich phosphorus center of the ligand enhances the catalytic activity of palladium in cross-coupling reactions of sterically demanding ortho-substituted aryl halides. In our study, we demonstrated the synthetic applicability of the new phosphine ligands in Buchwald-Hartwig and tosyl hydrazone coupling reactions.
- Sinai, ádám,Simkó, Dániel Cs.,Szabó, Fruzsina,Paczal, Attila,Gáti, Tamás,Bényei, Attila,Novák, Zoltán,Kotschy, András
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supporting information
p. 1122 - 1128
(2020/03/03)
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- Pyrrolo-imidazo[1,2- A[pyridine Scaffolds through a Sequential Coupling of N-Tosylhydrazones with Imidazopyridines and Reductive Cadogan Annulation, Synthetic Scope, and Application
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A new strategy for the construction of 3-phenyl-1H-pyrrolo-imidazo[1,2-a]pyridine backbone is described. The reaction starts from the coupling between N-tosylhydrazones and 2-chloro-3-nitroimidazo[1,2-a]pyridines leading to the formation of 3-nitro-2-(ary
- Zhang, Kena,El Bouakher, Abderrahman,Levaique, Helene,Bignon, Jerome,Retailleau, Pascal,Alami, Mouad,Hamze, Abdallah
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p. 13807 - 13823
(2019/10/16)
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- Toward a Greener Barluenga-Valdés Cross-Coupling: Microwave-Promoted C-C Bond Formation with a Pd/PEG/H2O Recyclable Catalytic System
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A green Barluenga-Valdés cross-coupling reaction for the synthesis of 1,1-diarylethylenes using palladium catalysis has been developed. The new catalytic system based on Pd/Xphos-SO3Na or Pd/MeDavephos-CF3SO3 in PEG/H2O under microwave irradiation was found to be the best conditions for this transformation. The recyclability of the palladium catalyst system was also studied, and it was found to be active over nine runs without significant loss in its activity.
- Lamaa, Diana,Messe, Estelle,Gandon, Vincent,Alami, Mouad,Hamze, Abdallah
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supporting information
p. 8708 - 8712
(2019/11/03)
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- Copper(i)-catalyzed benzylation of triazolopyridine through direct C-H functionalization
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A general and efficient copper-catalyzed benzylation reaction of triazolopyridine with N-tosylhydrazones was developed. This reaction forms a C(sp2)-C(sp3) bond through cross-coupling, and represents an exceedingly practical method t
- Reddy Lonka, Madhava,Zhang, Jinquan,Gogula, Thirupathi,Zou, Hongbin
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p. 7455 - 7460
(2019/08/20)
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- Selective Construction of 2-Substituted Benzothiazoles from o-Iodoaniline Derivatives S8 and N-Tosylhydrazones
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Selective construction of 2-substituted benzothiazoles from o-iodoaniline derivatives S8 and N-tosylhydrazone via a copper-promoted [3 + 1 + 1]-type cyclization reaction has been realized. In the protocol, the carbon atom on N-tosylhydrazone could be regulated to construct benzothiazole by changing the reaction system. Furthermore, the transformation has achieved the construction of multiple carbon-heteroatom bonds.
- Huang, Yubing,Zhou, Peiqi,Wu, Wanqing,Jiang, Huanfeng
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p. 2460 - 2466
(2018/02/23)
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- Cooperative Iodide Pd(0)-Catalysed Coupling of Alkoxyallenes and N-Tosylhydrazones: A Selective Synthesis of Conjugated and Skipped Dienes
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Palladium(0)-catalysed hydro-alkylation or -alkenylation of alkoxyallenes with N-tosylhydrazones gives direct access to conjugated and skipped 1-alkoxydienes with high efficiency and excellent functional-group compatibility. The reaction is proposed to in
- Parisotto, Stefano,Palagi, Lorenzo,Prandi, Cristina,Deagostino, Annamaria
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supporting information
p. 5484 - 5488
(2018/03/27)
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- Rhodium-Catalyzed B-H Bond Insertion Reactions of Unstabilized Diazo Compounds Generated in Situ from Tosylhydrazones
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Although transition-metal-catalyzed B-H bond insertion of carbenes into stable borane adducts has emerged as a promising method for organoborane synthesis, all the diazo compounds used to date as carbene precursors have had an electron-withdrawing group to stabilize them. Herein, we report a protocol for rhodium-catalyzed B-H bond insertion reactions of unstabilized diazo compounds generated in situ from tosylhydrazones. In addition, by using chiral dirhodium catalysts, we also achieved an asymmetric version of the reaction with good to excellent enantioselectivities (up to 98:2 e.r.). This is the first enantioselective heteroatom-hydrogen bond insertion reaction to use unstabilized diazo compounds as carbene precursors. The protocol exhibited good functional group tolerance and could be carried out on a gram scale. It also enabled one-pot transformation of a carbonyl group to a boryl group enantioselectively. The B-H bond insertion products could be easily transformed into chiral alcohols and other widely used organoboron reagents with enantiomeric fidelity.
- Pang, Yue,He, Qiao,Li, Zi-Qi,Yang, Ji-Min,Yu, Jin-Han,Zhu, Shou-Fei,Zhou, Qi-Lin
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supporting information
p. 10663 - 10668
(2018/09/06)
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- Palladium-catalyzed heck-type cascade cyclization of (Z)-1-iodo-1,6-dienes with N-tosyl hydrazones
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A palladium-catalyzed heck-type cascade cyclization of (Z)-1-iodo-1,6-dienes with N-tosyl hydrazones is reported. The alkylpalladium intermediate coupled with the diazo compound, generating the second alkylpalladium species bearing two β-H, which generate
- Li, Jun,Chi, Xiaochen,Meng, Long,Jiao, Luyang,Shang, Wenhui,Wang, Ping,Zhang, Daopeng,Dong, Yunhui,Liu, Qing,Liu, Hui
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supporting information
p. 7356 - 7360
(2018/10/24)
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- Directed C-C bond cleavage of a cyclopropane intermediate generated from: N -tosylhydrazones and stable enaminones: Expedient synthesis of functionalized 1,4-ketoaldehydes
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An efficient method to construct functionalized 1,4-ketoaldehydes bearing all-carbon α-quaternary centers via regioselective C-C bond activation has been described. The cyclopropanation of bench-stable enaminones with in situ generated diazo reagents from
- Ni, Meiyan,Zhang, Jianguo,Liang, Xiaoyu,Jiang, Yaojia,Loh, Teck-Peng
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supporting information
p. 12286 - 12289
(2017/11/20)
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- Palladium-Catalyzed One-Pot Synthesis of 5-(1-Arylvinyl)-1H-benzimidazoles: Overcoming the Limitation of Acetamide Partners
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A new one-pot palladium-catalyzed process between N-tosylhydrazones, N-(dihalophenyl)-imidates, and amines was designed. This reaction involves Barluenga cross-coupling and N-arylation followed by cyclization to produce functionalized benzimidazoles. Duri
- Naret, Timothée,Retailleau, Pascal,Bignon, Jér?me,Brion, Jean-Daniel,Alami, Mouad,Hamze, Abdallah
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supporting information
p. 1833 - 1847
(2016/06/09)
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- Pd-Catalyzed Highly Regio- and Stereoselective Formation of C-C Double Bonds: An Efficient Method for the Synthesis of Benzofuran-, Dihydrobenzofuran-, and Indoline-Containing Alkenes
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A highly regio- and stereoselective C-C double bond formation reaction via Pd-catalyzed Heck-type cascade process with N-tosylhydrazones has been developed. Various N-tosylhydrazones derived from both ketones and aldehydes are found to be efficient substrates to provide di- and trisubstituted olefins with high regio- and stereoselectivity. Furthermore, this reaction has a good functional group tolerance and different benzofuran-, dihydrobenzofuran-, and indoline-containing alkene products were obtained with high selectivity.
- Gao, Yang,Xiong, Wenfang,Chen, Huoji,Wu, Wanqing,Peng, Jianwen,Gao, Yinglan,Jiang, Huanfeng
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p. 7456 - 7467
(2015/08/18)
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- A direct facile and effective synthesis of various 1,1-heterodiaryl alkenes through Pd catalyzed cross coupling reaction using N-tosylhydrazones via C-OH bond activation
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At this event for the first time, the direct arylation with the generation of a facile and effective process for the synthesis of alkenes has been established through in situ C-OH activation afterward Pd catalyzed C-C bond formation of heteroarenols with
- Patel, Poojan K.,Dalvadi, Jignesh P.,Chikhalia, Kishor H.
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supporting information
p. 6585 - 6589
(2015/11/09)
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- Rhodium(III)-catalyzed ortho alkenylation of n-phenoxyacetamides with n-tosylhydrazones or diazoesters through C-H activation
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A coupling reaction of N-phenoxyacetamides with N-tosylhydrazones or diazoesters through RhIII-catalyzed C-H activation is reported. In this reaction, ortho-alkenyl phenols were obtained in good yields and with excellent regio- and stereoselectivity. Rh-c
- Hu, Fangdong,Xia, Ying,Ye, Fei,Liu, Zhenxing,Ma, Chen,Zhang, Yan,Wang, Jianbo
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supporting information
p. 1364 - 1367
(2014/03/21)
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- Copper-catalyzed aerobic oxidative transformation of ketone- Derived N-tosyl hydrazones: An entry to alkynes
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A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation.
- Li, Xianwei,Liu, Xiaohang,Chen, Huoji,Wu, Wanqing,Qi, Chaorong,Jiang, Huanfeng
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supporting information
p. 14485 - 14489
(2015/02/05)
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- An efficient one-pot synthesis of 3,5-diaryl-4-bromopyrazoles by 1,3-dipolar cycloaddition of in situ generated diazo compounds and 1-bromoalk-1-ynes
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A simple, highly efficient, one-pot synthesis of 3,5-di-aryl-4- bromopyrazoles via 1,3-dipolar cycloaddition of diazo compounds and alkynyl bromides has been developed. The diazo compounds and alkynyl bromides were generated in situ from tosylhydrazones and gem-dibromoalkenes, respectively. When ketone-derived hydrazones were used, 3,5-diaryl-4-bromo-3H-pyrazoles were obtained and the isomerization products 3,5-diaryl-4-bromo-1H-pyrazoles were formed when using aldehyde-derived hydrazones. The reaction system exhibited high regioselectivity and good functional group tolerance. Both electron-rich and electron-deficient-substituents on the aromatic ring of the hydrazones or the gem-dibromoalkenes gave desired products in moderate to good yields (67-86%). Georg Thieme Verlag Stuttgart - New York.
- Sha, Qiang,Wei, Yunyang
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supporting information
p. 413 - 420
(2013/03/14)
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- Copper-catalyzed direct benzylation or allylation of 1,3-azoles with N -tosylhydrazones
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Cu-Catalyzed cross-coupling of N-tosylhydrazones with 1,3-azoles leads to the direct C-H benzylation or allylation. Cu carbene migratory insertion is proposed to play the key role in this transformation.
- Zhao, Xia,Wu, Guojiao,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 3296 - 3299
(2011/04/24)
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