2113-57-7Relevant articles and documents
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Mowry et al.
, p. 1916 (1948)
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Synthesis and catalytic activity of nickel(II) complexes containing NCN pincer ligands
Nair, Ashwin G.,McBurney, Roy T.,Gatus, Mark R.D.,Walker, D.Barney,Bhadbhade, Mohan,Messerle, Barbara A.
, p. 63 - 70 (2017)
In this study, nickel(II) complexes [LmeNi(II)Cl]+(BPh4)?, [LmeNi(II)Cl]+(PF6)? and [Let2Ni(II)]+(BPh4)?2 were synthesised and characterized in the solution and solid states. Ligands Lme (C11H12N6) and Let (C13H17N6) featured a central carbene donor linked to pendant pyrazoles via either methylene or ethylene linkers. The catalytic activity of all three complexes was tested in the Kumada cross coupling reaction between phenylmagnesium bromide and aromatic halogen substituted substrates. [LmeNi(II)Cl]+(BPh4)?was found to be the most active catalyst.
The photochemistry of polyhaloarenes XIII. The photohydrodehalogenation of 3,4-dibromobiphenyl
Freeman, Peter K.,Jang, Jung-Suk,Haugen, Christian M.
, p. 8397 - 8406 (1996)
Irradiation of 3,4-dibromobiphenyl (BpBr2) in acetonitrile resulted in the formation of 4-bromobiphenyl (BpBr) and 3- bromobiphenyl (3-BpBr) in a ratio of 7.6 ± 0.1 up to 22% conversion of starting material. The dependence of the reciprocal of the quantum yield (1/Φ) upon 1/BpBr2 is linear. Reduction of BpBr2 with lithium di-tert-butylbiphenylide generates a 3.6:1.0 ratio of BpBr to 3-BpBr, while photohydrodebromination of BpBr2 in the presence of triethylamine produces a similar ratio of 1.8:1.0. Product determining radical stability was assessed by radical debromination of BpBr2 using Ph3SnH in THF, which resulted in a BpBr:3-BpBr ratio of 1.5:1.0 AMI calculations on the product determining radicals provide the basis for rationalization of products via excimer and radical anion intermediates.
Synthesis, Structure, and Chiroptical Properties of Indolo- and Pyridopyrrolo-Carbazole-Based C2-Symmetric Azahelicenes
Taniguchi, Taisei,Nishii, Yuji,Mori, Tadashi,Nakayama, Ken-ichi,Miura, Masahiro
supporting information, p. 7356 - 7361 (2021/04/26)
Treatment of 11,12-bis(1,1’-biphenyl-3-yl or 6-phenylpyridin-2-yl)-substituted 11,12-dihydro-indolo[2,3-a]carbazole with an oxidizing system of Pd(II)/Ag(I) induced effective double dehydrogenative cyclization to afford the corresponding π-extended azahelicenes. The optical resolutions were readily achieved by a preparative chiral HPLC. It was found that the pyridopyrrolo-carbazole-based azahelicene that contains four nitrogen atoms exhibits ca. 6 times larger dissymmetry factors both in circularly dichroism (CD) and circularly polarized luminescence (CPL), |gCD| and |gCPL| values being 1.1×10?2 and 4.4×10?3, respectively, as compared with the parent indolocarbazole-based azahelicene. Theoretical calculations at the RI-CC2 level were employed to rationalize the observed enhanced chiroptical responses. The (chir)optical properties of the former helicene was further tuned by a protonation leading to remarkable red-shift with a considerable enhancement of the |gCPL| value.
METHOD OF PRODUCING HALOGEN COMPOUND
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Paragraph 0052-0060, (2021/05/07)
PROBLEM TO BE SOLVED: To provide a method of efficiently producing an aromatic compound including a halogen group of interest. SOLUTION: A method of producing a halogen compound represented by the specified general formula (1) comprises reacting a compound represented by the specified general formula (2) with a compound represented by the specified general formula (3) in the presence of a transition metal compound, a phosphine compound being 1,1'-bis(diphenylphosphino)ferrocene or 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene, and a base. (In the formula, Ar1 and Ar2 represent organic groups; X represents a halogen group; Z represents a halogen group different than X; m represents an integer greater than or equal to 0; p represents an integer greater than or equal to 1; and each R represents a hydrogen atom, alkyl group or phenyl group, where the two R's may be linked together to form a ring.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
Switching from biaryl formation to amidation with convoluted polymeric nickel catalysis
Sen, Abhijit,Dhital, Raghu N.,Sato, Takuma,Ohno, Aya,Yamada, Yoichi M.A.
, p. 14410 - 14418 (2020/12/21)
A stable, reusable, and insoluble poly(4-vinyl-pyridine) nickel catalyst (P4VP-NiCl2) was prepared through the molecular convolution of poly(4-vinylpyridine) (P4VP) and nickel chloride. We proposed a coordination structure of the Ni center in the precatalyst based on elemental analysis and Ni K-edge XANES, and we confirmed that it is consistent with Ni K-edge EXAFS. The Suzuki?Miyaura-type coupling of aryl halides and arylboronic esters proceeded using P4VP-NiCl2 (0.1 mol % Ni) to give the corresponding biaryl compounds in up to 94% yield. Surprisingly, when the same reaction of aryl halides and arylboronic acid/ester was carried out in the presence of amides, the amidation proceeded predominantly to give the corresponding arylamides in up to 99% yield. In contrast, the reaction of aryl halides and amides in the absence of arylboronic acid/ester did not proceed. P4VP-NiCl2 successfully catalyzed the lactamization for preparing phenanthridinone. P4VP-NiCl2 was reused five times without significant loss of catalytic activity. Pharmaceuticals, natural products, and biologically active compounds were synthesized efficiently using P4VPNiCl2 catalysis. Nickel contamination in the prepared pharmaceutical compounds was not detected by ICP-MS analysis. The reaction was scaled to multigrams without any loss of chemical yield. Mechanistic studies for both Suzuki?Miyaura and amidation were performed.