Synthesis and reaction chemistry of boryliridium hydride complexes formed by oxidative addition of catecholborane to iridium(I): Lessons for metal-catalyzed hydroboration

2014 ◽  
Vol 750 ◽  
pp. 86-97 ◽  
Author(s):  
Joseph S. Merola ◽  
Joseph R. Knorr
Keyword(s):  
Oxidative Addition ◽  
Hydride Complexes ◽  
Metal Catalyzed

scholarly journals A radical approach to the copper oxidative addition problem: Trifluoromethylation of bromoarenes

Science ◽  
2018 ◽  
Vol 360 (6392) ◽  
pp. 1010-1014 ◽  
Author(s):  
Chip Le ◽  
Tiffany Q. Chen ◽  
Tao Liang ◽  
Patricia Zhang ◽  
David W. C. MacMillan
Keyword(s):  
Oxidative Addition ◽  
Open Shell ◽  
Past Century ◽  
Aryl Radical ◽  
Aryl Bromides ◽  
Addition Problem ◽  
Molecular Synthesis ◽  
Metal Catalyzed ◽  
High Valent ◽  
Radical Approach

Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.

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