Theoretical Study of the Copper-Catalyzed Hydroarylation of (Trifluoromethyl)alkyne with Phenylboronic Acid

The Journal of Organic Chemistry
Yoshihiko Yamamoto

Abstract

The copper-catalyzed hydroarylation of 1,1,1-trifluoro-2-butyne with phenylboronic acid was investigated by performing density functional theory calculations, and a plausible mechanism was proposed. The initial transmetalation step was first examined to compare the feasibility of the catalytically active copper species. Subsequently, the carbocupration of 1,1,1-trifluoro-2-butyne by the phenylcopper species was examined in terms of regioselectivity. The impacts of the alkyne terminal group and the para-substituents of phenylboronic acids on the carbocupration were also examined. Moreover, to shed light on the role of the electron-withdrawing groups on the alkyne substrates, the activation barrier for the carbocupration of 1,1,1-trifluoro-2-butyne was compared to those for several alkyne substrates bearing ester, ketone, cyano, and pentafluorophenyl groups, as well as 2-butyne, which has no electron-withdrawing group. The final protodecupration step involving methanol, acetic acid, or phenylboronic acid was examined to determine possible proton donors.

References

Jan 12, 2008·Accounts of Chemical Research·Yan Zhao, Donald G Truhlar
Jun 10, 2008·Chemical Communications : Chem Comm·Yoshihiko YamamotoYu Harada
Nov 29, 2008·Chemistry : a European Journal·Pao-Shun LinChien-Hong Cheng
Dec 5, 2008·Organic Letters·Yoshihiko Yamamoto, Naohiro Kirai
Jan 14, 2010·Journal of the American Chemical Society·Ryan E ShadeCraig A Merlic
Nov 12, 2010·Accounts of Chemical Research·Sebastian Kozuch, Sason Shaik
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk
Nov 25, 2011·Chemical Reviews·Naohiko Yoshikai, Eiichi Nakamura

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