896-65-1Relevant articles and documents
Stoichiometric C=O bond oxidative addition of benzophenone by a discrete radical intermediate to form a cobalt(I) carbene
Marquard, Seth L.,Bezpalko, Mark W.,Foxman, Bruce M.,Thomas, Christine M.
, p. 6018 - 6021 (2013)
Single electron transfer from the ZrIIICo0 heterobimetallic complex (THF)Zr(MesNPiPr2) 3Co-N2 (1) to benzophenone was previously shown to result in the isobenzopinacol product [(Ph2CO)Zr(MesNPiPr 2)3Co-N2]2 (2) via coupling of two ketyl radicals. In this work, thermolysis of 2 in an attempt to favor a monomeric ketyl radical species unexpectedly led to cleavage of the C-O bond to generate a Zr/Co μ-oxo species featuring an unusual terminal Co=CPh 2 carbene linkage, (η2-MesNPiPr 2)Zr(μ-O)(MesNPiPr2)2Co=CPh 2 (3). This complex was characterized structurally and spectroscopically, and its electronic structure is discussed in the context of density functional theory calculations. Complex 3 was also shown to be active toward carbene group transfer (cyclopropanation), and silane addition to 3 leads to PhSiH2O-Zr(MesNPiPr2)3Co-N 2 (5) via a proposed Co-alkyl bond homolysis route.
Electrochemical Ring-Opening Dicarboxylation of Strained Carbon-Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters
Liao, Li-Li,Wang, Zhe-Hao,Cao, Ke-Gong,Sun, Guo-Quan,Zhang, Wei,Ran, Chuan-Kun,Li, Yiwen,Chen, Li,Cao, Guang-Mei,Yu, Da-Gang
supporting information, p. 2062 - 2068 (2022/02/10)
Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of C-C single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of C-C single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.
Rhodium-Catalyzed Arylation of Cyclopropenes Based on Asymmetric Direct Functionalization of Three-Membered Carbocycles
Dian, Longyang,Marek, Ilan
supporting information, p. 3682 - 3686 (2018/03/06)
A variety of highly diastereo- and enantiomerically enriched arylcyclopropanes is obtained through the asymmetric rhodium-catalyzed arylation reaction of achiral nonfunctionalized cyclopropene derivatives with commercially available aryl boronic acids in the presence of (R,S)-Josiphos.
