438536-34-6Relevant academic research and scientific papers
Selective C-H Allylic Oxygenation of Cycloalkenes and Terpenoids Photosensitized by [Cu(Xantphos)(neoc)]BF4
Kallitsakis, Michael G.,Gioftsidou, Dimitra K.,Tzani, Marina A.,Angaridis, Panagiotis A.,Terzidis, Michael A.,Lykakis, Ioannis N.
, p. 13503 - 13513 (2021/09/13)
We present herein for the first time the use of the [Cu(Xantphos)(neoc)]BF4 as a photocatalyst for the selective C-H allylic oxygenation of cycloalkenes into the corresponding allylic hydroperoxides or alcohols in the presence of molecular oxygen. The proposed methodology affords the products at good yields and has also been applied successfully to several bioactive terpenoids, such as geraniol, linalool, β-citronellol, and phytol. A mechanistic study involving also kinetic isotope effects (KIEs) supports the proposed singlet oxygen-mediated reaction. On the basis of the high chemoselectivity and yields and the fast and clean reaction processes observed, the present catalytic system, [Cu(Xantphos)(neoc)]BF4, has also been applied to the synthesis, at a laboratory scale, of the cis-Rose oxide, a well-known perfumery ingredient used in rose and geranium perfumes.
Reductive desulfurization of allylic thiols by HS-/H2S in water gives clue to chemical reactions widespread in natural environments.
Hebting, Yanek,Adam, Pierre,Albrecht, Pierre
, p. 1571 - 1574 (2007/10/03)
The reduction of allylic thiols to alkenes by hydrogen sulfide in aqueous solutions, a novel reaction that may explain reduction processes widely occurring in natural environments, has been discovered. Its mechanism has been studied and suggested to follow an S(RN)1-like pathway involving radical intermediates undergoing 1,4 hydrogen shifts. [reaction: see text]
Photo-oxygenation of phytol and the structure revision of phytene-1,2-diol from Artemisia annua to phytene-1-ol-2-hydroperoxide
Wong, Ho-Fai,Brown, Geoffrey D.
, p. 30 - 33 (2007/10/03)
Photo-oxygenation of racemic phytol has yielded two secondary allylic hydroperoxides and an endoperoxide hemiacetal, which are the expected products from the "ene-type" reaction of singlet oxygen with the tri-substituted double bond in phytol. Spectral properties for one of the diastereoisomers of phytene-1-ol-2-hydroperoxide obtained from synthesis are shown to be identical with those of a natural product previously reported from Artemisia annua, which, it is concluded, was wrongly assigned as phytene-1,2-diol.
