557-31-3Relevant articles and documents
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Benedict,D.R. et al.
, p. 428 - 429 (1979)
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Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
supporting information, p. 1570 - 1573 (2014/04/17)
C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
Rate and product studies on the solvolyses of allyl chloroformate
Koh, Han Joong,Kang, Suk Jin
, p. 4117 - 4121 (2013/08/23)
The solvolysis rate constants of allyl chloroformate (CH 2=CHCH2OCOCl, 3) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the NT solvent nucleophilicity scale and YCl solvent ionizing scale, with the sensitivity values of 0.93 ± 0.05 and 0.41 ± 0.02 for l and m, respectively. These l and m values can be considered to support a S N2 reaction pathway. The activation enthalpies (ΔH≠) were 12.5 to 13.4 kcal·mol-1 and the activation entropies (ΔS≠) were -34.4 to -37.3 cal·mol-1·K -1, which is also consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effect (SKIE, kMeOH/k MeOD) of 2.16 was also in accord with the SN2 mechanism. The values of product selectivity (S) for the solvolyses of 3 in alcohol/water mixtures was 1.3 to 3.9, which is also consistent with the proposed bimolecular reaction mechanism.