scholarly journals Pd-Catalyzed Suzuki-Miyaura Cross-Coupling of Pentafluorophenyl Esters

Molecules ◽  
2018 ◽  
Vol 23 (12) ◽  
pp. 3134 ◽  
Author(s):  
Jonathan Buchspies ◽  
Daniel J. Pyle ◽  
Huixin He ◽  
Michal Szostak

Although the palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl esters has received significant attention, there is a lack of methods that utilize cheap and readily accessible Pd-phosphane catalysts, and can be routinely carried out with high cross-coupling selectivity. Herein, we report the first general method for the cross-coupling of pentafluorophenyl esters (pentafluorophenyl = pfp) by selective C–O acyl cleavage. The reaction proceeds efficiently using Pd(0)/phosphane catalyst systems. The unique characteristics of pentafluorophenyl esters are reflected in the fully selective cross-coupling vs. phenolic esters. Of broad synthetic interest, this report establishes pentafluorophenyl esters as new, highly reactive, bench-stable, economical, ester-based, electrophilic acylative reagents via acyl-metal intermediates. Mechanistic studies strongly support a unified reactivity scale of acyl electrophiles by C(O)–X (X = N, O) activation. The reactivity of pfp esters can be correlated with barriers to isomerization around the C(acyl)–O bond.

2020 ◽  
Vol 142 (7) ◽  
pp. 3564-3576 ◽  
Author(s):  
Antoine de Gombert ◽  
Alasdair I. McKay ◽  
Christopher J. Davis ◽  
Katherine M. Wheelhouse ◽  
Michael C. Willis

2017 ◽  
Vol 13 ◽  
pp. 2610-2616 ◽  
Author(s):  
Tao Fan ◽  
Wei-Dong Meng ◽  
Xingang Zhang

An efficient palladium-catalyzed Heck-type reaction of secondary trifluoromethylated alkyl bromides has been developed. The reaction proceeds under mild reaction conditions with high efficiency and excellent functional group tolerance, even towards formyl and hydroxy groups. Preliminary mechanistic studies reveal that a secondary trifluoromethylated alkyl radical is involved in the reaction.


ChemInform ◽  
2015 ◽  
Vol 46 (51) ◽  
pp. no-no
Author(s):  
Xin-Xing Wu ◽  
Si Chen ◽  
Wen-Long Chen ◽  
Li-Jing Wang ◽  
Pin Gao ◽  
...  

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