99856-26-5

Upstream product

• 2052-01-9 2-bromo-2-methylpropionic acid 
• 495-18-1 Benzohydroxamic acid 
• 211812-14-5 tert-butyl 2-(benzamidooxy)-2-methylpropanoate 

Downstream Products

• 15295-01-9 6,6-dimethyl-3-phenyl-[1,4,2]dioxazin-5-one 
• 88023-64-7 2-(aminooxy)-2-methylpropanoic acid 

Relevant academic research and scientific papers

Transition-Metal-Free Three-Component Radical 1,2-Amidoalkynylation of Unactivated Alkenes

A transition-metal-free radical 1,2-amidoalkynylation of unactivated alkenes is presented. α-Amido-oxy acids were used as amidyl radical precursors, which were oxidized by an organic photoredox catalyst (4CzlPN). The electrophilic N-radicals chemoselectively reacted with various aliphatic alkenes and the adduct radicals were then trapped by ethynylbenziodoxolone (EBX) reagents to eventually provide the amidoalkynylation products. These transformations, which were conducted under practical and mild conditions, showed high functional group tolerance and broad substrate scope. Mechanistic studies supported the radical nature of these cascades.

Radical Aza-Cyclization of α-Imino-oxy Acids for Synthesis of Alkene-Containing N-Heterocycles via Dual Cobaloxime and Photoredox Catalysis

Nitrogen-containing heterocycles are prevalent in both naturally and synthetically bioactive molecules. We report herein an unprecedented protocol for radical aza-cyclization of α-imino-oxy acids with pendant alkenes via synergistic photoredox and cobaloxime catalysis. With or without alkenes as the intermolecular cross-coupling partners, the transformation provides a variety of corresponding alkene-containing dihydropyrrole products in satisfactory yields. In the presence of external alkenes, the tandem reaction generates E-selective coupling products with excellent chemo- and stereoselectivity.

Anti-Markovnikov Radical Hydro- and Deuteroamidation of Unactivated Alkenes

Radical anti-Markovnikov hydro- and deuteroamidation of unactivated alkenes was achieved by merging photoredox and thiol catalysis. Reactions proceed by addition of the electrophilic CbzHN-radical (Cbz=carbobenzyloxy), readily generated by single-electron-transfer (SET) oxidation of an α-Cbz-amino-oxy acid to an alkene. The adduct radical is reduced by thiophenol added as an organic polarity reversal cocatalyst, which mediates the H transfer from H2O to the alkyl radical intermediate. Accordingly, deuteroamidation of alkenes was realized with excellent D incorporation by using D2O as the stoichiometric formal radical-reducing reagent. The reaction features low redox catalyst loading, excellent anti-Markovnikov selectivity, and the use of a large alkene excess is not required. Diverse Cbz-protected primary amines, including β-deuterated amines, can be obtained by applying this method.

Amidyl Radicals by Oxidation of α-Amido-oxy Acids: Transition-Metal-Free Amidofluorination of Unactivated Alkenes

A three-component transition-metal-free amidofluorination of unactivated alkenes and styrenes is presented. α-Amido-oxy acids are introduced as efficient and easily accessible amidyl radical precursors that are oxidized by a photoexcited organic sensitizer (Mes-Acr-Me) to the corresponding carboxyl radical. Sequential CO2 and aldehyde/ketone fragmentation leads to an N-centered radical that adds to an alkene. Commercial Selectfluor is used to trap the adduct radical through fluorine-atom transfer. The transformation features by high functional-group tolerance, broad substrate scope, and practical mild conditions. Mechanistic studies support the radical nature of the cascade.