69815-01-6Relevant academic research and scientific papers
Hydroxy-directed, fluoride-catalyzed epoxide hydrosilylation for the synthesis of 1,4-diols
Zhang, Yong-Qiang,Funken, Nico,Winterscheid, Peter,Gans?uer, Andreas
supporting information, p. 6931 - 6934 (2015/06/08)
Abstract A novel highly regioselective, fluoride-catalyzed hydrosilylation of β-hydroxy epoxides has been developed. The reaction is modular and applicable to the synthesis of a broad range of 1,4-diols. Fluoride is crucial for two reasons: First, it promotes the formation of a silyl ether (which contains a Si-H bond) and, second, it enables ring opening by an intramolecular SN2 reaction through activation of the silane. The reaction can be performed under air. A modular, convergent, and stereoselective synthesis of 1,4-diols by epoxide hydrosilylation has been developed (see scheme). The reaction occurs under fluoride catalysis, is high yielding, highly regioselective, and can be carried out on a large scale.
Direct synthesis of 1,4-diols from alkenes by iron-catalyzed aerobic hydration and C-H hydroxylation
Hashimoto, Takuma,Hirose, Daisuke,Taniguchi, Tsuyoshi
supporting information, p. 2730 - 2734 (2014/03/21)
Various 1,4-diols are easily accessible from alkenes through iron-catalyzed aerobic hydration. The reaction system consists of a user-friendly iron phthalocyanine complex, sodium borohydride, and molecular oxygen. Furthermore, the effect of additional ligands on the iron complex was examined for a model reaction. The second hydroxy group is installed by direct C(sp3)-H oxygenation, which is based on a [1,5] hydrogen shift process of a transient alkoxy radical that is formed by formal hydration of the olefin. One more hydroxy group: A method for the synthesis of 1,4-diols from simple alkenes has been developed. This unusual transformation entails an iron-catalyzed aerobic hydration and is achieved with convenient reagents, such as molecular oxygen. The formation of an intermediary alkoxy radical, which undergoes a [1,5] hydrogen shift, is likely to be essential for C(sp3)-H hydroxylation. Pc=phthalocyanine.
The reaction of alkyl peroxy radicals
Goosen, Andre,Kindermans, Sybrandus
, p. 1 - 8 (2007/10/03)
Secondary alkyl peroxy radicals generated from 4-phenyl-2-butyl-, 2-nonyl- and 3α-cholestanyl hydroperoxides at 45°C undergo Russell termination reactions in preference to non-terminating decomposition reactions. Non-terminating decomposition of 2-nonyl peroxy radicals afforded 2,5-nonanedione and 2,5-nonanediol due to intramolecular hydrogen abstraction reactions of alkoxy radicals. The radicals derived from 2-methyl-4-phenyl-2-butyl-, 2-methyl-5-phenyl-2-pentyl- and 2-methyl-6-phenyl-2-hexyl hydroperoxides afforded benzylic functionalized products due to intermolecular reactions. 2-Hexylperoxy radicals generated in excess alcohols ineffectively abstracted the α-hydrogens of alcohols. These results demonstrate the low reactivity of alkyl peroxy radicals.
