80287-86-1Relevant articles and documents
Stereospecific cyclopropanation reactions of stannyl-substituted acetals with alkenes via γ-elimination of tin
Sugawara, Masanobu,Yoshida, Jun-Ichi
, p. 1057 - 1058 (2007/10/03)
The reactions of stannyl substituted acetals with olefins resulted in the elimination of both the triorganostannyl group and the alkoxy group on the same carbon, and the production of the corresponding alkoxycyclopropanes in good yields. The stereospecifi
Effects of Substituents and Generation Methods on Insertion-Addition Selectivities of ''Arylcarbene'' in Alcohol-Olefin Binary Mixtures. Intervention of Reaction of Diazo Compounds Masquerading as Carbenes
Tomioka, Hideo,Suzuki, Shinji,Izawa, Yasuji
, p. 1047 - 1050 (2007/10/02)
A Hammett study of the insertion-addition selectivity (Ki/ka) and cyclopropanation stereoselectivity (kc/kt) of "arylcarbene" generated either photolytically or thermally in 2-propanol-ethyl vinyl ether binary mixtures showed that ρ values are highly sensitive to the generation method.Thus, plots of ki/ka and kc/kt vs. ? (?+) in the photolytic run gave ρ values of -0.96 (r = -0.96) and -0.15 (r = -0.95), respectively, whereas similar values are +1.4 (r = 0.93) and -1.1 (r = -0.96) in the thermal run.The results along with the effects of precursor, temperature, and sensitizer on the product distributions are interpreted as indicating that, while free carbene is involved in the photolytic run, the ground-state diazo compound is masquerading as carbene in its thermal reaction with the olefin.
