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The first straightforward strategy for the synthesis of 1,4-dicarbonyl -alkenes has been developed an electrochemical cross-coupling reaction of sulfoxonium ylides and alkynes with water. The metal-free protocol showed an easy-to-handle nature, good functional group tolerance, and high -stereoselectivity, which is rare in previous cases. The proposed reaction mechanism was convincingly established by carrying out a series of control experiments, cyclic voltammetry experiments, and density functional theory (DFT) studies.
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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11134330 | PMC |
http://dx.doi.org/10.1039/d4sc01141d | DOI Listing |
J Agric Food Chem
December 1999
Biocatalysts Ltd., Pontypridd, Mid-Glamorgan CF37 5UT, United Kingdom.
A number of products including apocarotenal, epoxycarotenal, apocarotenone, and epoxycarotenone generated by lipoxygenase (LOX) catalyzed co-oxidation of beta-carotene have been tentatively identified through the use of GC/MS and HPLC combined with photodiode array detection. Because of the large number of high molecular weight products detected and their probable chemical structures, a co-oxidation mechanism is proposed that involves random attack along the alkene chain of the carotenoid by a LOX-generated linoleoylperoxyl radical. It is suggested that a direct release from the enzyme of the radical, which initiates the co-oxidation of beta-carotene, is greater for pea LOX-3 than for pea LOX-2 or soybean LOX-1.
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