10596-01-7Relevant academic research and scientific papers
Reactions of cyclopalladated N-nitrosoanilines with SnIV reagents. Crystal structure of the bis cyclopalladated complex cis-Pd2
Albinati, Alberto,Affolter, Samuel,Pregosin, Paul S.
, p. 231 - 254 (1990)
A series of cyclopalladated N-methyl-N-nitrosoanilines, >2, X = OAc, Cl, Y = 4-OCH3, 4-CH3, 4-NO2, 5-CH3, have been prepared and treated with (i) a variety of reagents to afford mononuclear palladium(II) derivatives, and (ii) R13SnR2 to yield eventually 2-R2 substituted N-methyl-N-nitrosoanalines.The tin(IV) reagents, Me4Sn, Me3SnCCPh, Bun3SnCC(CH2)4CH3, Bun3SnCH=CH2, and Bun3SnCH2CH=CH2 all effectively transfer the R2 group to Pd, but, the mechanisms of the transfer reactions are not necessarily all the same.In some cases the presence of additional ligands, such as PPh3 or (Ph2PCH2)2, are required to suppress side reactions, especially the formation of the bis cyclopalladated complex cis-Pd2, 5.The crystal structure of 5 has been determined by X-ray diffraction methods; relevant bond distances (Angstroem) and bond angles (deg.) are: Pd-N(1) = 2.082(4), Pd-N(3) = 2.078(4); Pd-C(2) = 2.005(4); Pd-C(9) = 1.997(4); N(1)-Pd-N(3) = 99.7(2), N(1)-Pd-C(9) = 168.8(2), N(1)-Pd-C(2) = 79.5(2); C(2)-Pd-C(9) = 102.4(2).It is suggested that the formation of a specific coordination sphere, involving, one cyclometallated ligand, one weakly coordinated ligand, and a monodentate carbon ligand, such as CH3, leads to production of 5.
Rh(iii)-catalyzed, hydrazine-directed C-H functionalization with 1-alkynylcyclobutanols: A new strategy for 1: H -indazoles
Zhang, Lei,Chen, Junyu,Chen, Xiahe,Zheng, Xiangyun,Zhou, Jian,Zhong, Tianshuo,Chen, Zhiwei,Yang, Yun-Fang,Jiang, Xinpeng,She, Yuan-Bin,Yu, Chuanming
supporting information, p. 7415 - 7418 (2020/07/15)
Rh(iii)-catalyzed coupling of phenylhydrazines with 1-alkynylcyclobutanols was realized through a hydrazine-directed C-H functionalization pathway. This [4+1] annulation, based on the cleavage of a Csp-Csp triple bond in alkynylcyclobutanol, provides a new pathway to prepare diverse 1H-indazoles under mild reaction conditions. This journal is
Rhodium-catalyzed oxidative C-H/C-H cross-coupling of aniline with heteroarene: N-nitroso group enabled mild conditions
He, Shuang,Tan, Guangying,Luo, Anping,You, Jingsong
supporting information, p. 7794 - 7797 (2018/07/25)
The development of transition metal-catalyzed oxidative C-H/C-H cross-coupling between two (hetero)arenes to forge aryl-heteroaryl motifs under mild conditions is an appealing yet challenging task. Herein, we disclose a rhodium-catalyzed oxidative C-H/C-H cross-coupling reaction of an N-nitrosoaniline with a heteroarene under mild conditions. The judicious choice of the N-nitroso group as a directing group enables heightened reactivity. The coupled products could be transformed expediently to (2-aminophenyl)heteroaryl skeletons.
Rhodium(III)-Catalyzed Directed C?H Amidation of N-Nitrosoanilines and Subsequent Formation of 1,2-Disubstituted Benzimidazoles
Chen, Yanyu,Zhang, Rong,Peng, Qiujun,Xu, Lanting,Pan, XianHua
supporting information, p. 2804 - 2808 (2017/10/20)
An efficient rhodium-catalyzed direct C?H amidation of N-nitrosoanilines with 1,4,2-dioxazol-5-ones as amidating agents has been developed. This method featured mild reaction conditions, a wide substrate scope and satisfactory yields. Besides, the amidated products could be readily converted to pharmaceutically valuable 1,2-disubstituted benzimidazoles via an HCl-mediated deprotection/cyclization process in one pot.
Palladium-catalyzed ortho-acylation of N-Nitrosoanilines with α-oxocarboxylic acids: A convenient method to synthesize N-Nitroso ketones and indazoles
Zhang, Liang,Wang, Zhe,Guo, Peiyu,Sun, Wei,Li, Ya-Min,Sun, Meng,Hua, Chengwen
supporting information, p. 2511 - 2514 (2016/05/24)
An efficient and mild protocol for regioselective synthesis of N-Nitroso aryl ketones by palladium-catalyzed direct acylation of arenes using N-Nitroso as directing groups is described. This reaction proceeded smoothly and could tolerate a variety of functional groups. Moreover, this chemistry offers a convenient access to a range of indazoles.
Palladium-catalyzed oxidative C-H bond acylation of N-nitrosoanilines with toluene derivatives: A traceless approach to synthesize N-alkyl-2-aminobenzophenones
Wu, Yinuo,Feng, Ling-Jun,Lu, Xiao,Kwong, Fuk Yee,Luo, Hai-Bin
supporting information, p. 15352 - 15354 (2015/01/08)
A palladium-catalyzed cascade cross-coupling of N-nitroso-anilines and toluene derivatives for the direct synthesis of N-alkyl-2-aminobenzophenones is described. N-nitroso groups in anilines can act as the traceless directing groups while toluene derivatives can serve as effective acyl precursors under mild reaction conditions.
Rhodium(III)-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate for cycloaddition/fragmentation synthesis of indazoles
Chen, Jinsen,Chen, Pei,Song, Chao,Zhu, Jin
supporting information, p. 14245 - 14249 (2015/02/05)
RhIII-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N-nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C-H functionalization-based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tri-cyclic-fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.
