Journal of the American Chemical Society
Communication
(9) (a) Nguyen, J. D.; D’Amato, E. M.; Narayanam, J. M. R.;
Stephenson, C. R. J. Nat. Chem. 2012, 4, 854−859. (b) Larraufie, M.-
ACKNOWLEDGMENTS
■
The authors thank the EU (Grant PIIF-GA-20100274903 to
S.M.), the EPSRC and GSK (studentship to S.V.), the Skaggs-
Oxford Scholarship Program and NSF GRFP (predoctoral
fellowships to K.M.E), the Royal Thai Government (student-
ship to T.K.), and the BBSRC (studentship to M.O’D.) for
generous funding.
̂
H.; Pellet, R.; Fensterbank, L.; Goddard, J.-P.; Lacote, E.; Malacria, M.;
Ollivier, C. Angew. Chem., Int. Ed. 2011, 50, 4463−4466.
(c) Narayanam, J. M. R.; Tucker, J. W.; Stephenson, C. R. J. J. Am.
Chem. Soc. 2009, 131, 8756−8757.
(10) Tucker, J. W.; Nguyen, J. D.; Narayanam, J. M. R.; Krabbe, S.
W.; Stephenson, C. R. J. Chem. Commun. 2010, 46, 4985−4987.
(11) For a different approach (Cu-promoted trifluoromethylation of
prefunctionalized alkylboronic acids), see: Xu, J.; Xiao, B.; Xie, C.-Q.;
Luo, D.-F.; Liu, L.; Fu, Y. Angew. Chem., Int. Ed. 2012, 51, 12551−
12554.
(12) Boyle, W. J.; Bunnett, J. F. J. Am. Chem. Soc. 1974, 96, 1418−
1422.
(13) With Hantzsch ester, the reaction could not be further
optimized. We noted that the Umemoto reagent was completely
consumed at 45% conversion of the starting material (Table 1, entry
7).
REFERENCES
■
(1) The Chemistry of Double Bonded Functional Groups; Patai, S., Ed.;
Wiley: Chichester, U.K., 1997.
(2) (a) Crudden, C. M.; Edwards, D. Eur. J. Org. Chem. 2003, 4695−
4712. (b) Muniz, K. Chem. Soc. Rev. 2004, 33, 166−174. (c) Jacobsen,
̃
E. N.; Wu, M. H. Epoxidation of Alkenes Other Than Allylic Alcohols.
In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A.,
Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 18.2. (d) Marko,
I. E.; Svendsen, J. S. Dihydroxylation of Carbon−Carbon Double
Bonds. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz,
A., Yamamoto, H., Eds.; Springer: Berlin, 1999; Chapter 20.
(14) Lam, Y.-H.; Bobbio, C.; Cooper, I. R.; Gouverneur, V. Angew.
Chem., Int. Ed. 2007, 46, 5106−5110.
(15) (a) Yasu, Y.; Koike, T.; Akita, M. Angew. Chem., Int. Ed. 2012,
51, 9567−9571. For the conversion of styrenes into trifluoromethyl
ketones using trifluoromethylsulfonium triflate, see: (b) Zhang, C.-P.;
Wang, Z.-L.; Chen, Q.-Y.; Zhang, C.-T.; Gu, Y.-C.; Xiao, J.-C. Chem.
Commun. 2011, 47, 6632−6634.
(3) For a review of hydroalkylation reactions, see: (a) Den
Perez-Luna, A.; Chemla, F. Chem. Rev. 2010, 110, 2366−2447. For
selected examples of hydrofunctionalization, see: (b) Xiao, Y.-P.; Liu,
X.-Y.; Che, C.-M. Angew. Chem., Int. Ed. 2011, 50, 4937−4941.
(c) Urkalan, K. B.; Sigman, M. S. J. Am. Chem. Soc. 2009, 131, 18042−
18043. (d) DeLuca, R. J.; Sigman, M. S. J. Am. Chem. Soc. 2011, 133,
́ ̀
es, F.;
́
(16) Haga, M.; Dodsworth, E. S.; Eryavec, G.; Seymour, P.; Lever, A.
B. P. Inorg. Chem. 1985, 24, 1901−1906.
11454−11457. (e) Brown, T. J.; Weber, D.; Gagne,
Widenhoefer, R. A. J. Am. Chem. Soc. 2012, 134, 9134−9137.
́
M. R.;
(17) The absence of product resulting from oxytrifluoromethylation
suggests that oxidation of MeOH is more favorable than oxidation of
(4) For a unique example of conjugate addition to effect
hydrotrifluoromethylation of α,β-unsaturated acyl oxazolidinones,
see: (a) Erdbrink, H.; Peuser, I.; Gerling, U. I. M.; Lentz, D.;
Koksch, B.; Czekelius, C. Org. Biomol. Chem. 2012, 10, 8583−8586.
We demonstrated that this reaction is unsuitable for unactivated
alkenes, as ATRA occurred instead. Details are provided in the
Supporting Information. The photolysis of trifluoromethanethiosulfo-
nates or trifluorothioacetates in the presence of alkenes leads to a
mixture of (trifluoromethyl)alkanes and β-sulfanyl (trifluoromethyl)
alkanes. See: (b) Billard, T.; Roques, N.; Langlois, B. R. Tetrahedron
Lett. 2000, 41, 3069−3072. For examples of hydroperfluoroalkylation,
see: (c) Hu, C.-M.; Qiu, Y.-L. Tetrahedron Lett. 1991, 32, 4001−4002.
(d) Hu, C.-M.; Qiu, Y.-L. J. Org. Chem. 1992, 57, 3339−3342.
(e) Rong, X. X.; Pan, H.-Q.; Dolbier, W. R., Jr. J. Am. Chem. Soc. 1994,
116, 4521−4522. (f) Dolbier, W. R., Jr. Chem. Rev. 1996, 96, 1557−
1584. (g) Barata-Vallejo, S.; Postigo, A. J. Org. Chem. 2010, 75, 6141−
6148.
•
the carbon radical resulting from CF3 addition.
(18) While this manuscript was under review, a report disclosing the
silver-catalyzed hydrotrifluoromethylation of unactivated alkenes with
CF3SiMe3 appeared. See: Wu, X.; Chu, L.; Qing, F.-L. Angew. Chem.,
Int. Ed. 2013, DOI: 10.1002/anie.201208971.
(5) (a) Nguyen, J. D.; Tucker, J. W.; Konieczynska, M. D.;
Stephenson, C. R. J. J. Am. Chem. Soc. 2011, 133, 4160−4163.
(b) Parsons, A. T.; Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50,
9120−9123. (c) Xu, J.; Fu, Y.; Luo, D.-F.; Jiang, Y.-Y.; Xiao, B.; Liu, Z.-
J.; Gong, T.-J.; Liu, L. J. Am. Chem. Soc. 2011, 133, 15300−15303.
(d) Wang, X.; Ye, Y.; Zhang, S.; Feng, J.; Xu, Y.; Zhang, Y.; Wang, J. J.
Am. Chem. Soc. 2011, 133, 16410−16413. (e) Chu, L.; Qing, F.-L. Org.
Lett. 2012, 14, 2106−2109. (f) Iqbal, N.; Choi, S.; Kim, E.; Cho, E. J. J.
Org. Chem. 2012, 77, 11383−11387. (g) Li, Y.; Studer, A. Angew.
Chem., Int. Ed. 2012, 51, 8221−8224.
(6) (a) Muller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881−
̈
1886. (b) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem.
Soc. Rev. 2008, 37, 320−330. (c) O’Hagan, D. Chem. Soc. Rev. 2008,
37, 308−319. (d) Hagmann, W. K. J. Med. Chem. 2008, 51, 4359−
4369. (e) Jeschke, P. ChemBioChem 2004, 5, 570−589.
(7) For reviews, see: (a) Narayanam, J. M. R.; Stephenson, C. R. J.
Chem. Soc. Rev. 2011, 40, 102−113. (b) Teply, F. Collect. Czech. Chem.
́
Commun. 2011, 76, 859−917. (c) Tucker, J. W.; Stephenson, C. R. J. J.
Org. Chem. 2012, 77, 1617−1622. (d) Xuan, J.; Xiao, W.-J. Angew.
Chem., Int. Ed. 2012, 51, 6828−6838. For a review of radical
trifluoromethylation, see: (e) Studer, A. Angew. Chem., Int. Ed. 2012,
51, 8950−8958.
(8) Wallentin, C.-J.; Nguyen, J. D.; Finkbeiner, P.; Stephenson, C. R.
J. J. Am. Chem. Soc. 2012, 134, 8875−8884.
2508
dx.doi.org/10.1021/ja401022x | J. Am. Chem. Soc. 2013, 135, 2505−2508