88773-76-6Relevant articles and documents
Controlling Chemoselectivity of Catalytic Hydroboration with Light
Bergamaschi, Enrico,Chen, Yi-Kai,Hohenadel, Melissa,Lunic, Danijela,McLean, Liam A.,Teskey, Christopher J.
, (2022/01/13)
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
Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage-Independent Activation of Strong C-O Bonds
Stache, Erin E.,Ertel, Alyssa B.,Rovis, Tomislav,Doyle, Abigail G.
, p. 11134 - 11139 (2018/11/21)
Despite the prevalence of alcohols and carboxylic acids as functional groups in organic molecules and the potential to serve as radical precursors, C-O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen-centered nucleophile. We show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H atom trapping to afford the deoxygenated products. Using the same method, we demonstrate access to synthetically versatile acyl radicals, which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge C-O, C-N, and C-C bonds in a single step.
TBD-catalyzed direct 5- and 6-enolexo aldolization of ketoaldehydes
Ghobril, Cynthia,Sabot, Cyrille,Mioskowski, Charles,Baati, Rachid
supporting information; experimental part, p. 4104 - 4108 (2009/05/27)
Treatment of unfunctionalized acyclic ketoaldehydes with a catalytic amount of 1,5,7-triazabicyclo[4.4.0]dec-5-ene induces a direct intramolecular 5- and 6-enolexo aldolization, furnishing 2-ketocyclopentanols and 2-ketocyclohexanols in good-to-excellent yields. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.