94203-19-7

Upstream product

• 100-41-4 ethylbenzene 
• 1972-28-7 diethylazodicarboxylate 
• 15094-06-1 trans-ethylidenecyclohexene 
• 100-42-5 styrene 
• 25837-05-2 ethylbenzene-d10 

Downstream Products

• 1198417-28-5 C₁₇H₂₄N₂O₆ 

Relevant academic research and scientific papers

Selective Functionalization of Hydrocarbons Using a ppm Bioinspired Molecular Tweezer via Proton-Coupled Electron Transfer

An expanded porphyrin-biscopper hexaphyrin was introduced as a bioinspired molecular tweezer to co-catalyze functionalization of C(sp3)-H bonds. Theoretical and experimental investigations suggested that the biscopper hexaphyrin served as a molecular tweezer to mimic the enzymatic orientation/proximity effect, efficiently activating the N-hydroxyphthalimide (NHPI) via light-free proton-coupled electron transfer (PCET), at an exceptionally low catalyst loading of 10 mol ppm. The resulting N-oxyl radical (PINO) was versatile for chemoselective C-H oxidation and amination of hydrocarbons.

N-Hydroxybenzimidazole as a structurally modifiable platform forN-oxyl radicals for direct C-H functionalization reactions

Methods for direct functionalization of C-H bonds mediated byN-oxyl radicals constitute a powerful tool in modern organic synthesis. While severalN-oxyl radicals have been developed to date, the lack of structural diversity for these species has hampered further progress in this field. Here we designed a novel class ofN-oxyl radicals based onN-hydroxybenzimidazole, and applied them to the direct C-H functionalization reactions. The flexibly modifiable features of these structures enabled facile tuning of their catalytic performance. Moreover, with these organoradicals, we have developed a metal-free approach for the synthesis of acyl fluoridesviadirect C-H fluorination of aldehydes under mild conditions.

Radical amination of C(sp3)-H bonds using N -hydroxyphthalimide and dialkyl azodicarboxylate

A direct conversion of C(sp3)-H bonds to C(sp3)-N bonds has been achieved by utilizing catalytic N-hydroxyphthalimide (NHPI) and stoichiometric dialkyl azodicarboxylate. NHPI functions as a precursor of the electron-deficient phthalimide N-oxyl radical (PINO) to abstract hydrogens, and dialkyl azodicarboxylate acts as a trapping agent of the resultant carbon radical to generate the hydrazine derivatives. This C-H amination proceeds in a highly chemoselective manner with a wide applicability to functionalize benzylic, propargylic, and aliphatic C-H bonds. Furthermore, the obtained hydrazine compounds were readily converted to the corresponding carbamates or amines. Hence, the present protocol for direct introduction of the nitrogen functionality serves as a powerful tool for efficient construction of nitrogen-substituted natural products and pharmaceuticals.

Synthesis of carbamates from diethoxycarbonyl hydrazine derivatives by E1cB eliminative cleavage of the N-N′-bond rather than reduction

[Chemical Equation Presented] Treatment of diethoxycarbonyl hydrazine derivatives with methyl bromoacetate/Cs2CO3/MeCN at 50°C followed by heating to 80°C resulted in N-N′ bond cleavage to the corresponding carbamates.

Ene Reactions of Conjugated Dienes. 2. Dependence of Rate on Degree of Hydrogen Removed and s-Cis or s-Trans Diene Character

The rates of the ene reactions between diethyl diazenedicarboxylate and a number of dienes have been measured and product structures determined.Accelerated reactions are observed with 1,3-cyclohexadienes but not with dienes held fixed in the s-trans form.Within the first set of systems tertiary hydrogens are much more reactive than secondary.Within the second set secondary are (in turn) more reactive than primary.There is no apparent correlation between the rate of the Diels-Alder reaction of the 1,3-cyclohexadienes with maleic anhydride and the rate of ene reaction with the diazenedicarboxylate.