1029-73-8Relevant academic research and scientific papers
Triplet-Triplet Fluorescence and Spin Polarization of 1- and 2-Naphthylphenylcarbenes
Despres, Alain,Migirdicyan, Eva,Haider, Karl,Maloney, Vincent M.,Platz, Matthew S.
, p. 6632 - 6637 (1990)
The fluorescence spectra of 1- and 2-naphthylphenylcarbenes (1-NPC and 2-NPC) dispersed in liquid and solid solutions have been studied as a function of temperature, concentration, host, and sample history by laser flash photolysis and conventional spectr
Enantioselective Diarylcarbene Insertion into Si-H Bonds Induced by Electronic Properties of the Carbenes
Evans, Declan,Houk, K. N.,Li, Mao-Lin,Li, Wen-Tao,Xu, Bin,Yang, Liang-Liang,Zhou, Qi-Lin,Zhu, Shou-Fei
, p. 12394 - 12399 (2020/08/06)
Catalytic enantioselection usually depends on differences in steric interactions between prochiral substrates and a chiral catalyst. We have discovered a carbene Si-H insertion in which the enantioselectivity depends primarily on the electronic characteristics of the carbene substrate, and the log(er) values are linearly related to Hammett parameters. A new class of chiral tetraphosphate dirhodium catalysts was developed; it shows excellent activity and enantioselectivity for the insertion of diarylcarbenes into the Si-H bond of silanes. Computational and mechanistic studies show how the electronic differences between the two aryls of the carbene lead to differences in energies of the diastereomeric transition states. This study provides a new strategy for asymmetric catalysis exploiting the electronic properties of the substrates.
gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors
Hu, Mingyou,Ni, Chuanfa,Li, Lingchun,Han, Yongxin,Hu, Jinbo
, p. 14496 - 14501 (2015/11/27)
A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.
