1857-74-5Relevant articles and documents
Rotational Preference in "Cage" Dissociation-Recombinations: Thermal Automerization of Optically Active Methyl threo-2,3-Diphenylbutane-2-carboxylate
Doering, W. von E.,Birladeanu, Ludmila
, p. 7442 - 7444 (1986)
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Ang,H.-G. et al.
, p. 4841 - 4846 (1963)
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Radical Organometallic Phase-transfer Reactions
Galamb, Vilmos,Alper, Howard
, p. 88 - 89 (1983)
The phase-transfer catalysed coupling reactions of benzylic halides, in the presence of catalytic quantities of bis(dibenzylideneacetone)palladium(0) or cobalt carbonyl, proceed via radical pathways.
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Light,Zeiss
, p. 517,527 (1970)
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Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates
Li, Qi Yukki,Gockel, Samuel N.,Lutovsky, Grace A.,DeGlopper, Kimberly S.,Baldwin, Neil J.,Bundesmann, Mark W.,Tucker, Joseph W.,Bagley, Scott W.,Yoon, Tehshik P.
, p. 94 - 99 (2022/01/11)
Reactions that enable carbon–nitrogen, carbon–oxygen and carbon–carbon bond formation lie at the heart of synthetic chemistry. However, substrate prefunctionalization is often needed to effect such transformations without forcing reaction conditions. The development of direct coupling methods for abundant feedstock chemicals is therefore highly desirable for the rapid construction of complex molecular scaffolds. Here we report a copper-mediated, net-oxidative decarboxylative coupling of carboxylic acids with diverse nucleophiles under visible-light irradiation. Preliminary mechanistic studies suggest that the relevant chromophore in this reaction is a Cu(ii) carboxylate species assembled in situ. We propose that visible-light excitation to a ligand-to-metal charge transfer (LMCT) state results in a radical decarboxylation process that initiates the oxidative cross-coupling. The reaction is applicable to a wide variety of coupling partners, including complex drug molecules, suggesting that this strategy for cross-nucleophile coupling would facilitate rapid compound library synthesis for the discovery of new pharmaceutical agents. [Figure not available: see fulltext.].
Decatungstate Catalyzed Synthesis of Trifluoromethylthioesters from Aldehydes via a Radical Process
Ye, Zhegao,Lei, Ziran,Ye, Xiaodong,Zhou, Liejin,Wang, Yanan,Yuan, Zheliang,Gao, Feng,Britton, Robert
supporting information, p. 765 - 775 (2021/12/17)
Here we report a mild and general method for the trifluoromethylthiolation of aldehydes using N-trifluoromethylthiosaccharin as the CF3S radical source and sodium decatungstate (NaDT) as the photocatalyst. This reaction proceeds via hydrogen at
Reactivity of (bi-Oxazoline)organonickel Complexes and Revision of a Catalytic Mechanism
Ju, Luchuan,Lin, Qiao,LiBretto, Nicole J.,Wagner, Clifton L.,Hu, Chunhua Tony,Miller, Jeffrey T.,Diao, Tianning
, p. 14458 - 14463 (2021/09/18)
Bi-Oxazoline (biOx) has emerged as an effective ligand framework for promoting nickel-catalyzed cross-coupling, cross-electrophile coupling, and photoredox-nickel dual catalytic reactions. This report fills the knowledge gap of the organometallic reactivity of (biOx)Ni complexes, including catalyst reduction, oxidative electrophile activation, radical capture, and reductive elimination. The biOx ligand displays no redox activity in (biOx)Ni(I) complexes, in contrast to other chelating imine and oxazoline ligands. The lack of ligand redox activity results in more negative reduction potentials of (biOx)Ni(II) complexes and accounts for the inability of zinc and manganese to reduce (biOx)Ni(II) species. On the basis of these results, we revise the formerly proposed “sequential reduction” mechanism of a (biOx)Ni-catalyzed cross-electrophile coupling reaction by excluding catalyst reduction steps.
