42522-59-8Relevant articles and documents
Biosynthesis of the insect pheromone (S)-4-methyl-3-heptanone
Jarvis, Andrew P.,Liebig, Juergen,Hoelldobler, Bert,Oldham, Neil J.
, p. 1196 - 1197 (2004)
Using stable isotope-labelled probes and mass spectrometry, the insect pheromone (S)-4-methyl-3-heptanone is shown to be biosynthesised from three propionate units following a polyketide/fatty acid-type metabolic route.
Effect of isotopic substitution on the electron spin dynamics of the CH3C(COOH)2 radical in X-irradiated methyl malonic acid powder: Intrinsic potentials and activation energies
Sornes,Benetis,Erickson,Mahgoub,Eberson,Lund
, p. 8987 - 8994 (1997)
The temperature-dependent EPR line shapes from the methyl rotor of the X irradiation-induced CH3C(COOH)2 radical in powder MMA (methyl malonic acid) and the X irradiation-induced radical CD3C(COOH)2 in methyl-specifically deuterated powder MMA are studied experimentally for the temperature range 4.8 K (5 K) to 77 K (65 K). The hydrogenated system is simulated using a quantum inertial dynamical model with a hindering potential and three-site exchange rotation. The deuterated system is simulated using a classical three-site exchange model. The results show that due to the increase in moment of inertia, the tunneling frequency is negligible for the deuterated rotor, resulting in a stopped rotor low-temperature spectrum, while being sufficiently large for the hydrogenated system for this to exhibit tunneling. From the low-temperature deuterated analogue spectrum, the potential twist angle is estimated to δ = ±50°±2° (+n·60°, n∈Z). The site-exchange activation energy of the deuterium rotor is observed to be 387 K, substantially lower than the hindering potential depth of 618 K. The hydrogenated system exchange rotation rate assumes a linear behavior with 754 K activation energy in the classical region of temperatures above 50 K.
High-valent palladium-promoted formal Wagner-Meerwein rearrangement
Wu, Hongmiao,Yang, Bin,Zhu, Lin,Lu, Ronghua,Li, Guigen,Lu, Hongjian
supporting information, p. 5804 - 5807 (2016/11/29)
An oxy-palladation, formal Wagner-Meerwein rearrangement and fluorination cascade has been established for generating fluorinated oxazolidine-2,4-diones and oxazolidin-2-ones. The reaction has a broad substrate scope in which both aryl and alkyl groups can be utilized as efficient migrating groups. Experimental evidence suggests that the reaction is initiated by anti-oxy-palladation of the olefin, followed by oxidative generation of an alkyl PdIV intermediate and a concerted migration-fluorination.
