Journal of the American Chemical Society
Article
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1
removed for centrifugation. The products were analyzed by H NMR
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spectroscopy and GC−MS. In the reaction, 2.20 mmol of 1,2-
bis(trifluoroacetyl)ethane was formed. 1H NMR: 1,2-bis-
(trifluoroacetyl)ethane δ 4.49 (4H, H2C−O2CCF3). Reactions without
added chloride also led to similar reactivity. Under the same
conditions, these reactions yielded 11% glycol and 21% of what is
tentatively assigned as 1-trifluoroacetyl-2-iodoethane. 1H NMR: 1-
trifluoroacetyl-2-iodoethane δ 4.44 (2H, H2C−O2CCF3, t, 3JH−H = 6.8
37−49.
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3
Hz), 3.17 (2H, H2C−I, t, JH−H = 6.8 Hz)
Propane Functionalization. In a typical reaction with propane, a
stir bar, 0.676 mmol of KCl, 7.7 mmol of NH4IO3, and 8.0 mL of
HTFA were loaded into the reactor. After the reactor was sealed, it was
purged three times with propane and finally charged with 830 kPa
propane (3.0 mmol of propane). The reactor was weighed and
subsequently heated and stirred (800 rpm) for 2 h. The reactor was
removed from the heating block and cooled to room temperature. The
resultant gas was collected in a gas bag and analyzed by GC-TCD. A
standard consisting of 30 μL of HOAc was added to the reaction
liquid. The mixture was stirred, after which a sample was removed for
centrifugation. The products were analyzed by 1H NMR spectroscopy
and GC−MS. In the reaction, 121 μmol of 1-propyl trifluoroacetate,
404 μmol of 2-propyl trifluoroacetate, and 236 μmol of 1,2-
propanediyl bis(trifluoroacetate) were formed. 1H NMR: 1-propyl
trifluoroacetate δ 4.17 (2H, H2C−O2CCF3, t, 3JH−H = 7 Hz), 1.59 (2H,
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3
CH2CH3, m), 0.79 (3H, CH3, t, JH−H = 7 Hz); 2-propyl
3
trifluoroacetate δ 4.17 (1H, HC−O2CCF3, h, JH−H = 6 Hz), 1.18
3
(6H, CH3, d, JH−H = 6 Hz); 1,2-propanediyl bis(trifluoroacetate) δ
5.27 (1H, HC−O2CCF3, m), 4.38 (1H, H2C−O2CCF3, dd, 2JH−H = 12
Hz, 3JH−H = 3 Hz), 4.27 (1H, H2C−O2CCF3, dd, 2JH−H = 12 Hz, 3JH−H
3
= 7 Hz), 1.26 (3H, CH3, d, JH−H = 7 Hz).
(20) Lorkovic, I. M.; Sun, S.; Gadewar, S.; Breed, A.; Macala, G. S.;
Sardar, A.; Cross, S. E.; Sherman, J. H.; Stucky, G. D.; Ford, P. C. J.
Phys. Chem. A 2006, 110, 8695−8700.
ASSOCIATED CONTENT
* Supporting Information
Supporting figures, tables, and spectra. This material is available
■
(21) Olah, G. A.; Gupta, B.; Felberg, J. D.; Ip, W. M.; Husain, A.;
Karpeles, R.; Lammertsma, K.; Melhotra, A. K.; Trivedi, N. J. J. Am.
Chem. Soc. 1985, 107, 7097−7105.
S
(22) Ding, K.; Metiu, H.; Stucky, G. D. ACS Catal. 2013, 3, 474−
477.
AUTHOR INFORMATION
(23) Gunay, A.; Theopold, K. H. Chem. Rev. 2010, 110, 1060−1081.
(24) Nelson, A. P.; DiMagno, S. G. J. Am. Chem. Soc. 2000, 122,
8569−8570.
■
Corresponding Authors
(25) Gormisky, P. E.; White, M. C. J. Am. Chem. Soc. 2013, 135,
14052−14055.
Notes
(26) Stoian, S. A.; Xue, G.; Bominaar, E. L.; Que, L., Jr.; Munck, E. J.
̈
The authors declare no competing financial interest.
Am. Chem. Soc. 2014, 136, 1545−1558.
(27) Hintermair, U.; Sheehan, S. W.; Parent, A. R.; Ess, D. H.;
Richens, D. T.; Vaccaro, P. H.; Brudvig, G. W.; Crabtree, R. H. J. Am.
Chem. Soc. 2013, 135, 10837−10851.
ACKNOWLEDGMENTS
■
This work was solely supported as part of the Center for
Catalytic Hydrocarbon Functionalization, an Energy Frontier
Research Center funded by the U.S. Department of Energy,
Office of Science, Office of Basic Energy Sciences, under Award
DE-SC0001298.
(28) Liu, W.; Huang, X.; Cheng, M.-J.; Nielsen, R. J.; Goddard, W. A.,
III; Groves, J. T. Science 2012, 337, 1322−1325.
(29) Liu, W.; Groves, J. T. Angew. Chem., Int. Ed. 2013, 52, 6024−
6027.
(30) Liu, W.; Groves, J. T. J. Am. Chem. Soc. 2010, 132, 12847−
12849.
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