35096-45-8Relevant articles and documents
Sulfamate Esters Guide Selective Radical-Mediated Chlorination of Aliphatic C?H Bonds
Short, Melanie A.,Blackburn, J. Miles,Roizen, Jennifer L.
, p. 296 - 299 (2018)
Masked alcohols are particularly appealing as directing groups because of the ubiquity of hydroxy groups in organic small molecules. Herein, we disclose a general strategy for aliphatic γ-C(sp3)?H functionalization guided by a masked alcohol. Specifically, we determine that sulfamate ester derived nitrogen-centered radicals mediate 1,6-hydrogen-atom transfer (HAT) processes to guide γ-C(sp3)?H chlorination. This reaction proceeds through a light-initiated radical chain-propagation process and is capable of installing chlorine atoms at primary, secondary, and tertiary centers.
δ-C-H Mono- And Dihalogenation of Alcohols
Herron, Alastair N.,Liu, Dongxin,Xia, Guoqin,Yu, Jin-Quan
supporting information, p. 2766 - 2770 (2020/02/13)
Alkoxy radicals have long been known to enable remote C-H functionalization via 1,5-hydrogen atom abstraction. However, methods for their generation traditionally have relied upon highly oxidizing metals, ultraviolet radiation, or preformed peroxide intermediates, which has prevented the development of many desirable transformations. Herein we report a new bench-stable precursor that decomposes to free alkoxy radicals via a previously unreported single-electron oxidation pathway. This new precursor enables the fluorination and chlorination of remote C-H bonds under exceptionally mild conditions with exceedingly high monoselectivity. Iterative use of this precursor enables the introduction of a second halogen atom, granting access to remote dihalide motifs, including CF2 and CFCl.
Oxidation of aliphatic alcohols with the lead tetraacetate - Metal halide system under mechanical activation
Kapustina,Sokova,Makhaev,Borisov,Nikishin
, p. 1842 - 1845 (2007/10/03)
The mechanochemical oxidation of n-pentanol, n-hexanol, and n-octanol with the Pb(OAc)4 - MHal system (M = Li, K; Hal = Cl, Br) in the absence of a solvent affords esters, and secondary alcohols with the composition C8H17OH and C9H19OH give ketones.