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Synthesis of allylic trifluoromethanes


Recent Literature

An efficient copper-catalyzed allylic trifluoromethylation reaction of alkenes with a hypervalent iodine (III) reagent (Togni reagent) provides a general and straightforward way to synthesize allylic trifluoromethylated compounds under mild conditions.
X. Wang, Y. Ye, S. Zhang, J. Feng, Y. Xu, Y. Zhang, J. Wang, J. Am. Chem. Soc., 2011, 133, 16410-16413.

Phenyl bromodifluoroacetate as bench-stable trifluoromethylation reagent converts readily available alcohols to trifluoromethanes in a Cu-catalyzed deoxytrifluoromethylation reaction. This reaction should be useful for a variety of medicinal, agricultural, and materials chemists.
F. de Azambuja, S. M. Lovrien, P. Ross, B. R. Amber, R. A. Altman, J. Org. Chem., 2019, 84, 2061-2071.

A copper-catalyzed decarboxylation of allylic bromodifluoroacetates enables the conversion of allylic alcohols to trifluoromethanes in two steps. Preliminary mechanistic studies distinguish this reaction from previously reported Cu-mediated reactions.
B. R. Ambler, R. A. Altman, Org. Lett., 2013, 15, 5578-5581.

An efficient copper-catalyzed trifluoromethylation of polysubstituted alkenes assisted by decarboxylation of β,γ-unsaturated carboxylic acids provides allylic and vinylic CF3-substituted compounds under mild conditions.
Z. He, P. Tan, J. Hu, Org. Lett., 2016, 18, 72-75.

An organic photoredox-catalyzed dehydroxylative trifluoromethylation of allylic alcohols with readily available CF3SO2Na provides multifunctionalized CF3-allylic compounds in high yields and excellent stereoselectivity. In this environmentally benign reaction, the in situ generated byproduct SO2 activates the C-OH bond.
B. Li, W. Zeng, L. Wang, Z. Geng, T.-P. Loh, P. Xie, Org. Lett., 2021, 23, 5235-5240.

Cu(CH3CN)4BF4 catalyzes a radical bis(trifluoromethylation) of alkynes and 1,3-enynes with Togni reagent II and (bpy)Zn(CF3)2 at room temperature to afford the corresponding 1,2-bis(trifluoromethylated) alkenes and 1,4-bis(trifluoromethylated) allenes in good yields. This protocol exhibits broad substrate scope and excellent functional group compatibility.
H. Shen, H. Xiao, L. Zhu, C. Li, Synlett, 2020, 31, 41-44.

A practical, convenient, and highly regioselective copper-catalyzed 1,4-chlorotrifluoromethylation of 1,3-enynes affords chloro- and CF3-containing tetrasubstituted allene derivatives with very good yield. A 1,4-bromotrifluoromethylation is also reported.
J. Huang, Y. Jia, X. Li, J. Duan, Z.-X. Jiang, Z. Yang, Org. Lett., 2021, 23, 2314-2319.


A cobalt-catalyzed photochemical synthesis of allylic trifluoromethanes from styrene derivatives using 2,2,2-trifluoroethyl iodide complements existing approaches, providing an alternative bond construction strategy to access these compounds. The process may be conducted in continuous mode in a photochemical flow reactor.
L. M. Kreis, S. Krautwald, N. Pfeiffer, R. E. Martin, E. M. Carreira, Org. Lett., 2013, 15, 1634-1637.

A nickel-catalyzed hydrotrifluoroalkylation of terminal alkynes provides allylic trifluoromethyl terminal alkenes with high efficiency, broad substrate scope, and favorable functional group compatibility. The combination of nitrogen and phosphine ligands, especially electron-rich ones, plays an indispensable role in the course of the reaction.
T. Zhang, Y.-W. Zuo, R.-X. Jin, Y.-F. Zhang, B.-B. Wu, X.-S. Wang, Org. Lett., 2023, 25, 3578-3584.