88-67-5Relevant articles and documents
Perfluoroalkyl Cobaloximes: Preparation Using Hypervalent Iodine Reagents, Molecular Structures, Thermal and Photochemical Reactivity
Liebing, Phil,Oehler, Florian,Wagner, Mona,Tripet, Pascal F.,Togni, Antonio
, p. 570 - 583 (2018)
Treatment of cobaloximes(II), [Co(Hdmg)2(L)2] (Hdmg = dimethylglyoximate, L = neutral ligand), with perfluoroalkyl iodane reagents leads to the formation of perfluoroalkyl cobaloximes(III), [CoRF(Hdmg)2(L)] (RF = CF3, C2F5, n-C3F7, CF2CF2Ph; L = Py, NH3, MeNH2, PhNH2, MeOH). The synthetic protocol can be significantly simplified to a one-pot procedure starting from cobalt(II) acetate-tetrahydrate. The products have been fully characterized by NMR, IR, and UV/vis spectroscopy as well as single-crystal X-ray diffraction, and the thermal and photochemical reactivity has been studied. According to the Co-L distances in the crystal, the trans influence of the RF- ligands can be rated as C2F5- ≈ n-C3F7- 2CF2Ph- ≈ CF3- 3-. The thermal decomposition of the complexes is different from that of nonfluorinated analogues, probably including perfluoroalkylation of an Hdmg- ligand as the initial step. In the CF3 complexes, the Co-C bond is very resistant against photolysis, but the ligand L is readily exchanged by MeOH upon exposure to blue light. In the complexes with longer RF chains, the Co-C bond is more readily cleaved, and the product distribution depends strongly on the presence of O2. Thus, the alkane RFH is the main product under exclusion of O2, while a fluorinated methyl ester and HF are formed in a methanol solution exposed to air.
Togni-II Reagent Mediated Selective Hydrotrifluoromethylation and Hydrothiolation of Alkenes?
Teng, Shuang,Meng, Lingkui,Xu, Bingbing,Tu, Guangsheng,Wu, Peng,Liao, Zhiwen,Tan, Yulin,Guo, Jian,Zeng, Jing,Wan, Qian
supporting information, p. 3429 - 3434 (2021/11/08)
Based on the redox reactions of Togni-II reagent and thiols, a thiol-tuned selective functionalization of unactivated olefins was disclosed. In combination with aryl thiols, stoichiometric amount of Togni-II reagent prompted a hydrotrifluoromethylation of alkenes, in which, aryl thiols played as reductant and hydrogen source; while by utilization of alkyl thiols, catalytic amount of Togni-II reagent initiated thiol-ene and thiol-yne reactions. The reported applications are characterized by their operational simplicity and wide functional group tolerance.
N-Alkenylation of hydroxamic acid derivatives with ethynyl benziodoxolone to synthesizecis-enamides through vinyl benziodoxolones
Shimbo, Daisuke,Maruyama, Toshifumi,Tada, Norihiro,Itoh, Akichika
supporting information, p. 2442 - 2447 (2021/04/02)
The stereoselective synthesis ofcis-β-N-alkoxyamidevinyl benziodoxolones (cis-β-N-RO-amide-VBXs) fromO-alkyl hydroxamic acids in the presence of an ethynyl benziodoxolone-acetonitrile complex (EBX-MeCN) is reported herein. The reaction was performed under mild conditions including an aqueous solvent, a mild base, and room temperature. The reaction tolerated variousO-alkyl hydroxamic acids derived from carboxylic acids, such as amino acids, pharmaceuticals, and natural products. Vinyl dideuteratedcis-β-N-MeO-amide-VBXs were also synthesized using deuterium oxide as the deuterium source. Valine-derivedcis-β-N-MeO-amide-VBX was stereospecifically derivatized to hydroxamic acid-derivedcis-enamides without the loss of stereoselectivity or reduction in the deuterium/hydrogen ratio.