The Journal of Organic Chemistry
Note
(17) Sygula, A.; Rabideau, P. W. J. Am. Chem. Soc. 1998, 120, 12666.
(18) Seiders, T. J.; Siegel, J. S. J. Am. Chem. Soc. 1999, 121, 7804.
(19) Reed, C. A.; Fackler, N. L. P.; Kim, K.-C.; Stasko, D.; Evans, D.
R. J. Am. Chem. Soc. 1999, 121, 6314.
(20) Reed, C. A.; Kim, K.-C.; Stoyanov, E. S.; Stasko, D.; Tham, F. S.;
Mueller, L. J.; Boyd, P. D. W. J. Am. Chem. Soc. 2003, 125, 1796.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the Swiss National Science Foundation for financial
support.
REFERENCES
■
(1) For a review on H/D exchange reactions and the relevance of
deuterated products, see: Atzrodt, J.; Derdau, V.; Fey, T.;
Zimmermann, J. Angew. Chem., Int. Ed. 2007, 46, 7744.
(2) For a review on the preparation of deuterated compounds, see:
Junk, T.; Catallo, W. J. Chem. Soc. Rev. 1997, 26, 401.
(3) For a review on metal-catalyzed H/D exchange, see: Lockley, W.
J. S., Heys, J. R., Eds. J. Label. Cmpd. Radiopharm. 2010, 53 (Special
issue), 635.
(4) For recent reports on transition metal-mediated H/D exchange,
see: (a) Hickman, A. J.; Cismesia, M. A.; Sanford, M. S.
Organometallics 2012, 31, 1761. (b) Rhinehart, J. L.; Manbeck, K.
A.; Buzak, S. K.; Lippa, G. M.; Brennessel, W. W.; Goldberg, K. I.;
Jones, W. D. Organometallics 2012, 31, 1943. (c) Groll, B.; Schnurch,
̈
̈
M.; Mihovilovic, M. D. J. Org. Chem. 2012, 77, 4432. (d) Di Giuseppe,
A.; Castarlenas, R.; Perez-Torrente, J. J.; Lahoz, F. J.; Polo, V.; Oro, L.
́
A. Angew. Chem., Int. Ed. 2011, 50, 3938. (e) Feng, Y.; Jiang, B.; Boyle,
P. A.; Ison, E. A. Organometallics 2010, 29, 2857. (f) Derdau, V.;
Atzrodt, J.; Zimmermann, J.; Kroll, C.; Bruckner, F. Chem.Eur. J.
̈
2009, 15, 10397.
(5) Acid-catalyzed H/D exchange: (a) Boix, C.; Poliakoff, M.
Tetrahedron Lett. 1999, 40, 4433. (b) Shabanova, E.; Schaumburg, K.;
Kamounah, F. S. J. Chem. Res., Synop. 1999, 364.
(6) Lewis acid catalyzed H/D exchange: Prechtl, M. H. G.;
Teltewskoi, M.; Dimintrov, A.; Kemnitz, E.; Braun, T. Chem. Eur. J.
2011, 14385.
(7) Base-catalyzed H/D exchange: Yao, J.; Evilia, R. F. J. Am. Chem.
Soc. 1994, 116, 364.
(8) H/D exchange in supercritical water: (a) Kalpala, J.; Hartonen,
K.; Huhdanpaa, M.; Riekkola, M. Green Chem. 2003, 5, 670. (b) Siskin,
̈
̈
M.; Katritzky, A. R. Chem. Rev. 2001, 101, 825.
(9) For reviews on carborane acids, see: (a) Reed, C. A. Acc. Chem.
Res. 2010, 43, 121. (b) Reed, C. A. Chem. Commun. 2005, 1669.
(10) For the preparation of arenium acids, see: (a) Reed, C. A.; Kim,
K.-C.; Stoyanov, E. S.; Stasko, D.; Tham, F. S.; Mueller, L. J.; Boyd, P.
D. W. J. Am. Chem. Soc. 2003, 125, 1796. (b) Reed, C. A.; Fackler, N.
L. P.; Kim, K.-C.; Stasko, D.; Evans, D. R. J. Am. Chem. Soc. 1999, 121,
6314.
(11) The formation of [Mes−H][Al(OC(CF3)3)4] and its
conversion to the thermally more stable [Mes−H][((CF3)3CO)3Al−
F−Al(OC(CF3)3)3] has very recently been reported: Kraft, A.; Beck,
J.; Steinfeld, G.; Scherer, H.; Himmel, D.; Krossing, I. Organometallics
2012, 31, 7485.
(12) Our first observation of this scrambling came during isotopic
labeling studies toward understanding the formation of a beta-silyl
stabilized allyl cation, see: Duttwyler, S.; Zhang, Y.; Linden, A.; Reed,
C. A.; Baldridge, K. K.; Siegel, J. S. Angew. Chem. 2009, 48, 3747.
(13) Biemann, K. Mass Spectrometry: Organic Chemical Applications;
McGraw Hill: New York, 1962.
(14) Isotopologs are compounds with the same chemical structure
that differ only in their isotope composition (e.g., [1,2-D2]propane and
[1,2,3-D3]propane). The term isotopomer indicates isotopologs with
the same mass, e.g., [1,1-D2]propane and [1,2-D2]propane: IUPAC
Compendium of Chemical Terminology, 2nd ed.; McNaught, A.
D.,Wilkinson, A., Eds.; Blackwell Scientific Publications: Cambridge,
1997.
(15) Butterfield, A. M.; Gilomen, B.; Siegel, J. S. Org. Process Res. Dev.
2012, 16, 664.
(16) For a complementary method to introduce deuterium labeling
under basic condition, see: Greene, A. K.; Scott, L. T. J. Org. Chem.
2012, ASAP publication ahead of print; DOI: 10.1021/jo301903m.
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