Organic Letters
Letter
Scheme 6. Preliminary Mechanistic Studies
AUTHOR INFORMATION
Corresponding Authors
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ORCID
Author Contributions
∥W.-K.T. and Z.-W.X. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We gratefully acknowledge financial support from the National
Natural Science Foundation of China (Nos. 21571047,
21502038, 21402036, 21472033) and CPSF (2016M600478,
2017T100444).
Scheme 7. Proposed Mechanism
REFERENCES
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(1) (a) Kirsch, P. Synthesis Reactivity Applications. Modern
Fluoroorganic Chemistry 2013, 117, 1464. (b) He, Z.; Luo, T.; Hu, M.;
Cao,Y.;Hu,J.Angew.Chem.,Int.Ed.2012,51,3944.(c)Li,G.;Wang,T.;
Fei,F.;Su,Y.-M.;Li,Y.;Lan,Q.;Wang,X.-S. Angew.Chem.,Int.Ed.2016,
55, 3491. (d) Chen, Q.; Wang, C.; Zhou, J.; Wang, Y.; Xu, Z.; Wang, R. J.
Org. Chem. 2016, 81, 2639. (e) Zhang, H.-R.; Chen, D.-Q.; Han, Y.-P.;
Qiu, Y.-F.; Jin, D.-P.; Liu, X.-Y. Chem. Commun. 2016, 52, 11827.
́
(f) Bacauanu, V.; Cardinal, S.; Yamauchi, M.; Kondo, M.; Fernandez, D.
F.;Remy,R.;MacMillan,D.W.C.Angew.Chem.,Int.Ed.2018,57,12543.
(g)Dong, X.;WenYang, W.;Hu, W.;Sun, J. Angew. Chem., Int. Ed. 2015,
54, 660.
(2) (a) Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.; Zhu, W.; Acena, J. L.;
̃
Soloshonok, V. A.; Izawa, K.; Liu, H. Chem. Rev. 2016, 116, 422.
(b)Swallow,S.Chem.Soc.Rev.2008,37,320.(c)Gillis,E.P.;Eastman,K.
J.; Hill, M. D.; Donnelly, D. J.; Meanwell, N. A. J. Med. Chem. 2015, 58,
8315.
(3) (a) Dutheuil, G.; Couve-Bonnaire, S.; Pannecoucke, X. Angew.
Chem.,Int.Ed.2007,46,1290.(b)Tredwell,M.;Luft,J.A.R.;Schuler,M.;
Tenza, K.; Houk, K. N.; Gouverneur, V. Angew. Chem., Int. Ed. 2008, 47,
357. (c) Audouard, C.; Barsukov, I.; Fawcett, J.; Griffith, G. A.; Percy, J.
M.; Pintat, S.; Smith, C. A. Chem. Commun. 2004, 1526.
and the key intermediate ethyl α-monofluoroacetate radical
C,15b,16 which in turn add to the alkene to afford radical D.13b
Subsequently, the radical D donates one electron to [CoII]·B to
produce the cationic complex F, which loses a proton to produce
alkene product 3. Finally, the reaction of [CoI]·E with ethyl
bromofluoroacetate 2a would regenerate intermediate A and
thereby complete the catalytic cycle.
Insummary,wehavedevelopedavisiblelightmediatedmethod
for the synthesis of allyl monofluorides by activating ethyl
bromofluoroacetate using (triphenyltin)cobaloxime as the
photocatalyst. A series of styrene derivatives were subjected to
the present reaction conditions and furnished the corresponding
monofluoromethylated alkenes in good yields and with excellent
E/Z selectivity. Besides, the simple reaction condition, such as
room temperature and without the need of base or reductant,
make the present work a potential useful method for further
modification of biologically active compounds.
(4) (a) Hassan, A. E. A.; Shuto, S.; Matsuda. Nucleosides Nucleotides
1994, 13, 197. (b)Herreros, E.;Almela, M. J.;Lozano, S.;GomezDeLas
Heras, F.; Gargallo-Viola, D. Antimicrob. Agents Chemother. 2001, 45,
3132. (c) Khan, M. O. F.; Lee, H. Chem. Rev. 2008, 108, 5131.
(5)(a)Katcher, M.H.;Doyle, A.G. J. Am.Chem. Soc.2010,132,17402.
(b) Katcher, M. H.; Sha, A.; Doyle, A. G. J. Am. Chem. Soc. 2011, 133,
15902. (c) Benedetto, E.; Tredwell, M.; Hollingworth, C.;
Khotavivattana, T.; Brown, J. M.; Gouverneur, V. Chem. Sci. 2013, 4, 89.
(6) (a) Li, Y.; Liu, J.; Zhang, L.; Zhu, L.; Hu, J. J. Org. Chem. 2007, 72,
5824. (b) Murakami, S.; Ishii, H.; Fuchigami, T. J. Fluorine Chem. 2004,
125, 609. (c) Caillot, G.; Dufour, J.; Belhomme, M.-C.; Poisson, T.;
Grimaud, L.; Pannecoucke, X.; Gillaizeau, I. Chem. Commun. 2014, 50,
5887. (d) Belhomme, M.-C.; Poisson, T.; Pannecoucke, X. Org. Lett.
2013, 15, 3428. (e) Yu, C.; Iqbal, N.; Park, S.; Cho, E. Chem. Commun.
2014,50,12884.(f)Feng,Z.;Min,Q.Q.;Zhao,H.Y.;Gu,J.W.;Zhang,X.
Angew. Chem.,Int.Ed. 2015,54,1270.(g)Feng,Z.;Xiao,Y.-L.;Zhang,X.
Org. Chem. Front. 2016, 3, 466. (h)Xu, H.;Wang, D.;Chen, Y.;Wan, W.;
Deng, H.; Ma, K.; Wu, S.; Hao, J.; Jiang, H. Org. Chem. Front. 2017, 4,
1239.(i)Wang,X.;Zhao,S.;Liu,J.;Zhu,D.;Guo,M.;Tang,X.;Wang,G.
Org. Lett. 2017, 19, 4187. (j) Wei, X.-J.; Boon, W.; Hessel, V.; Noel, T.
ACS Catal. 2017, 7, 7136.
ASSOCIATED CONTENT
* Supporting Information
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S
TheSupportingInformationisavailablefreeofchargeontheACS
Experimental procedures and NMR spectra (PDF)
D
Org. Lett. XXXX, XXX, XXX−XXX