610-97-9Relevant articles and documents
Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage
Powers, David C.,Lee, Eunsung,Ariafard, Alireza,Sanford, Melanie S.,Yates, Brian F.,Canty, Allan J.,Ritter, Tobias
, p. 12002 - 12009 (2012)
Oxidation of binuclear Pd(II) complexes with PhICl2 or PhI(OAc)2 has previously been shown to afford binuclear Pd(III) complexes featuring a Pd-Pd bond. In contrast, oxidation of binuclear Pd(II) complexes with electrophilic trifluoromethylating ("CF3 +") reagents has been reported to afford mononuclear Pd(IV) complexes. Herein, we report experimental and computational studies of the oxidation of a binuclear Pd(II) complex with "CF3 +" reagents. These studies suggest that a mononuclear Pd(IV) complex is generated by an oxidation-fragmentation sequence proceeding via fragmentation of an initially formed, formally binuclear Pd(III), intermediate. The observation that binuclear Pd(III) and mononuclear Pd(IV) complexes are accessible in the same reactions offers an opportunity for understanding the role of nuclearity in both oxidation and subsequent C-X bond-forming reactions.
Mechanochemical-Cascaded C-N Cross-Coupling and Halogenation Using N-Bromo- And N-Chlorosuccinimide as Bifunctional Reagents
Bera, Shyamal Kanti,Mal, Prasenjit
, p. 14144 - 14159 (2021/09/13)
Exploration of alternative energy sources for chemical transformations has gained significant interest from chemists, and mechanochemistry is one of those sources. Herein, we report the use of N-bromosuccinimides (NBS) and N-chlorosuccinimides (NCS) as bifunctional reagents for a cascaded C-N bond formation and subsequent halogenation reactions. Under the solvent-free mechanochemical (ball-milling) conditions, the synthesis of a wide range of phenanthridinone derivatives from N-methoxy-[1,1′-biphenyl]-2-carboxamides is accomplished. During the reactions, NBS and NCS first assisted the oxidative C-N coupling reaction and subsequently promoted a halogenation reaction. Thus, the role of NBS and NCS was established to be bifunctional. Overall, a mild, solvent-free, convenient, one-pot, and direct synthesis of various bromo- and chloro-substituted phenanthridinone derivatives was achieved.
Lipshutz-type bis(amido)argentates for directed: Ortho argentation
Tezuka, Noriyuki,Hirano, Keiichi,Peel, Andrew J.,Wheatley, Andrew E. H.,Miyamoto, Kazunori,Uchiyama, Masanobu
, p. 1855 - 1861 (2020/03/03)
Bis(amido)argentate (TMP)2Ag(CN)Li2 (3, TMP-Ag-ate; TMP = 2,2,6,6-tetramethylpiperidido) was designed as a tool for chemoselective aromatic functionalization via unprecedented directed ortho argentation (DoAg). X-Ray crystallographic analysis showed that 3 takes a structure analogous to that of the corresponding Lipshutz cuprate. DoAg with this TMP-Ag-ate afforded multifunctional aromatics in high yields in processes that exhibited high chemoselectivity and compatibility with a wide range of functional groups. These included organometallics- A nd transition metal-susceptible substituents such as methyl ester, aldehyde, vinyl, iodo, (trifluoromethanesulfonyl)oxy and nitro groups. The arylargentates displayed good reactivity with various electrophiles. Chalcogen (S, Se, and Te) installation and azo coupling reactions also proceeded efficiently.