Hemiaminals of trifluoroacetaldehyde, as trifluoromethylating agents

doi:10.1016/S0040-4039(99)01369-6

Tetrahedron Letters

Volume 40, Issue 35, 27 August 1999, Pages 6411-6414

https://doi.org/10.1016/S0040-4039(99)01369-6 Get rights and content

Abstract

Hemiaminals of trifluoroacetaldehyde are new trifluoromethylating agents. These reagents are synthesised from amines and gaseous trifluoroacetaldehyde. tBuONa is able to deprotonate the hemiaminals to form trifluoromethyl anion equivalents CF₃CH(O⁻)NMe₂. The trifluoromethyl anion has been transferred from such intermediates to benzaldehyde yielding phenyl (trifluoromethyl) methanol.

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References (8)

B. Folleas et al.
Tetrahedron Lett.
(1998)
H. Molines et al.
J. Fluorine. Chem.
(1980)
D.M. Wiemers et al.
J. Am. Chem. Soc.
(1986)
G.A. Olah et al.
Synthetic Fluorine Chemistry

There are more references available in the full text version of this article.

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Hemiaminals of trifluoroacetaldehyde, as trifluoromethylating agents

Abstract

Tetrahedron Lett.

J. Fluorine. Chem.

J. Am. Chem. Soc.

Synthetic Fluorine Chemistry