Controlling Chemoselectivity of Catalytic Hydroboration with Light
The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction of a functional handle fo
Bergamaschi, Enrico,Chen, Yi-Kai,Hohenadel, Melissa,Lunic, Danijela,McLean, Liam A.,Teskey, Christopher J.
(2022/01/13)
Oxidative carbon-carbon bond cleavage is a key step in spiroacetal biosynthesis in the fruit fly Bactrocera cacuminata
The early steps of spiroacetal biosynthesis in the fruit fly Bactrocera cacuminata (Solanum fly) have been investigated using a series of deuterium-labeled, oxygenated fatty acid like compounds. These potential spiroacetal precursors were administered to male flies, and their volatile emissions were analyzed for specific deuterium incorporation by GC/MS. This has allowed the order of early oxidative events in the biosynthetic pathway to be determined. Together with the already well-established later steps, the results of these in vivo investigations have allowed essentially the complete delineation of the spiroacetal biosynthetic pathway, beginning from products of primary metabolism. A fatty acid equivalent undergoes a series of enzyme-mediated oxidations leading to a trioxygenated fatty acid like species that includes a vicinal diol. This moiety then undergoes enzyme-mediated oxidative carbon-carbon bond cleavage as the key step to generate the C9 unit of the final spiroacetal. This is the first time such an oxidative transformation has been reported in insects. A final hydroxylation step is followed by spontaneous spiro-cyclization. This distinct pathway adds further to the complexity and diversity of biosynthetic pathways to spiroacetals.
Singh, Arti A.,Rowley, Jessica A.,Schwartz, Brett D.,Kitching, William,De Voss, James J.
p. 7799 - 7821
(2015/03/18)
Selektivitaet der anodischen Oxidation von CH- und CH2-Gruppen; selektive Oxidation von Steroiden an C-6
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Hembrock, Annegret,Schaefer, Hans J.,Zimmermann, Gesine