Categories: C-C Bond Formation > Heteroatom-containing Molecules, Chains > Trifluoromethylation
Synthesis of allylic trifluoromethanes
| Related: |
 |
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.
Related
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.