Kinetics on Formation of Hyperbranched Poly(ethyl methacrylate) via a Controlled Radical Mechanism of Photofunctional Inimer

2003 ◽  
Vol 36 (10) ◽  
pp. 3505-3510 ◽  
Author(s):  
Koji Ishizu ◽  
Takeshi Shibuya ◽  
Susumu Kawauchi
2010 ◽  
Vol 46 (26) ◽  
pp. 4698 ◽  
Author(s):  
Ben Newland ◽  
Hongyun Tai ◽  
Yu Zheng ◽  
Diego Velasco ◽  
Andrea Di Luca ◽  
...  

2009 ◽  
Vol 42 (14) ◽  
pp. 4960-4962 ◽  
Author(s):  
Lei Tao ◽  
Jingquan Liu ◽  
B. H. Tan ◽  
Thomas P. Davis

2020 ◽  
Author(s):  
Josh MacMillan ◽  
Katherine Marczenko ◽  
Erin Johnson ◽  
Saurabh Chitnis

The addition of Sb-H bonds to alkynes was reported recently as a new hydroelementation reaction that exclusively yields anti-Markovnikov <i>Z</i>-olefins from terminal acetylenes. We examine four possible mechanisms that are consistent with the observed stereochemical and regiochemical outcomes. A comprehensive analysis of solvent, substituent, isotope, additive, and temperature effects on hydrostibination reaction rates definitively refutes three ionic mechanisms involving closed-shell charged intermediates. Instead the data support a fourth pathway featuring neutral radical Sb<sup>II</sup> and Sb<sup>III</sup> intermediates. Density Functional Theory (DFT) calculations are consistent this model, predicting an activation barrier that is within 1 kcal mol<sup>-1</sup> of the experimental value (Eyring analysis) and a rate limiting step that is congruent with experimental kinetic isotope effect. We therefore conclude that hydrostibination of arylacetylenes is initiated by the generation of stibinyl radicals, which then participate in a cycle featuring Sb<sup>II</sup> and Sb<sup>III</sup> intermediates to yield the observed <i>Z</i>-olefins as products. This mechanistic understanding will enable rational evolution of hydrostibination as a methodology for accessing challenging products such as <i>E</i>-olefins.


Author(s):  
Arumugavel Murugan ◽  
Venkata Nagarjuna Babu ◽  
Nagaraj Sabarinathan ◽  
Sharada Duddu. S

Here we report a visible-light-promoted metal-free regioselective C3-H trifluoromehtylation reaction that proceeds via radical mechanism and which supported by control experiments. The combination of photoredox catalysis and hypervalent iodine reagent provides a practical approach for the present trifluoromethylation reaction and synthesis of a library of trifluoromethylated indazoles.


ACS Omega ◽  
2021 ◽  
Vol 6 (4) ◽  
pp. 3390-3398
Author(s):  
Kyung Il Kim ◽  
Robin Lawler ◽  
Hyun June Moon ◽  
Pavithra Narayanan ◽  
Miles A. Sakwa-Novak ◽  
...  

Author(s):  
Matthieu P. J. Miclotte ◽  
Stefan B. Lawrenson ◽  
Spyridon Varlas ◽  
Bilal Rashid ◽  
Emma Chapman ◽  
...  

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