Decarboxylation efficiency of carboxylic acids as ligands of metal oxide nanocluster resists upon γ-ray irradiation

Metal oxide nanocluster resists have recently attracted considerable attention for use in extreme ultraviolet (EUV) lithography. To obtain sophisticated guidelines for material design, it is necessary to understand well the radiation-induced chemical reaction scheme including the insolubilization mechanism. In this study, the production of CO2, which is considered to be one of the end products of treatment with an ionizing radiation, was investigated for eight types of carboxylic acid under various conditions using -rays (60Co) as a radiation source. The amount of CO2 produced was measured by gas chromatography (GC). GCO2 (/100 eV), which indicates decarboxylation efficiency, was evaluated. CO2 was generated through electron addition, hole transfer, and hydroxyl radical addition to the molecular and ionic forms of carboxylic acids. The dependences of GCO2 on reaction partners were clarified. The dependences of GCO2 on the molecular structure and dissociative state of carboxylic acids were also clarified.

Radical Addition of Hydroxy Quinazolines and Alkylation of Quinones via the Electro-induced Homolysis of 4-Alkyl-1,4-dihydropyridines

Herein, we report the formation of C(sp3)-centered radicals via the electro-induced homolysis of 4-alkyl-1,4-dihydropyridines (alkyl-DHPs). The resulting alkyl radicals reacted with hydroxy quinazolines or quinones to afford 2-alkyl dihydroquinazolinones or alkylated quinones. A broad range of alkyl DHPs could be used as versatile radical precursors under electrolysis conditions. This alterative strategy provided a simple and effective pathway for the construction of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds under mild conditions.

Synthesis of Isoquinoline-1,3(2H,4H)-diones by Visible-light-mediated the Cyclization of Acryloylbenzamides with Alkyl Boronic Acids, Arylsulfonylhydrazides and Oxime Esters

An efficient visible-light-mediated tandem reaction of acryloylbenzamides with alkyl boronic acids, arylsulfonylhydrazides and oxime esters is developed. The reaction proceeds the radical addition and cyclization to give various isoquinoline-1,3(2H,4H)-diones in satisfactory yields under mild conditions, which provides a good opportunity to discover new meaningful bioactive compounds.

Planar Blatter radicals through Bu3SnH and TMS3SiH–assisted cy-clization of aryl iodides: Azaphilic radical addition

Bu3SnH and TMS3SiH–assisted cyclizations of iodoarene derivatives of the benzo[e][1,2,4]triazine lead to the formation of planar Blatter radicals (2-phenyl-3H-[1,2,4]triazino[5,6,1-kl]phenoxazin-3-yls and 2-phenyl-3H-[1,2,4]triazino[5,6,1-kl]phenothiazin-3-yls) in yields up to 96%. The cyclization step involves...

Cyanomethylative cyclization of unactivated alkenes with nitriles for the synthesis of cyano-containing ring-fused quinazolin-4(3H)-ones

The synthesis of cyano-containing ring-fused quinazolin-4(3H)-one derivatives was developed under metal-free conditions. This reaction undergoes radical C(sp3)-H functionalization of alkyl nitriles, cascade radical addition/cyclization with N-alkylated quinazolinones to deliver the...

Mn-Mediated Alpha-Radical Addition of Carbonyls to Olefins: Systematic Study, Scope, and Electrocatalysis

A systematic study of the manganese-mediated alpha-radical addition of carbonyl groups to olefins is presented. After an in-depth investigation of the parameters that govern the reaction, a first round of optimization allowed the development of a unified stoichiometric set of conditions which was subsequently assessed during the exploration of the scope. Due to observed limitations, the knowledge accumulated during the initial study was reengaged to quickly optimize promising substrates that were so far inaccessible under previously reported conditions. Altogether these results led to the creation of a predictive model based on the pKa of the carbonyl compound and both the substitution and geometry of the alkene coupling partner. Finally, a departure from the use of stoichiometric manganese was enabled through the development of a robust and practical electrocatalytic version of the reaction.