Organic Letters
Letter
the operational complexity of its synthesis, see: Fookson, A.;
Pomerantz, P.; Rich, E. H. J. Res. Natl. Bur. Stand. 1951, 47, 31−34.
(7) For reviews of hydrometalation chemistry, see: (a) Brown, H. C.
Organic Synthesis via Organoboranes; Wiley: New York, 1975.
(b) Burgess, K.; Ohlmeyer, M. Chem. Rev. 1991, 91, 1179−1191. (c)
Matteson, D. S. Stereodirected Synthesis with Organoboranes; Springer:
New York, 1995; Chapter 2. (d) Wipf, P.; Kendall, C. Top. Organomet.
Chem. 2004, 8, 1−25. (e) Chen, J.; Guo, J.; Lu, Z. Chin. J. Chem. 2018,
36, 1075−1109.
monitoring of both the model reaction and the B(C6F5)3-
catalyzed decomposition of surrogate 8, no HD gas evolution
In conclusion, we have reported the metal-free hydro-
deuteration of alkenes using a cyclohexa-1,4-diene-based
surrogate of HD gas. The stepwise mechanism provides a
solution to the long-standing problem of achieving high levels of
regioselectivity in hydrodeuteration chemistry. This represents a
useful addition to the collection of methods for the isotopic
labeling of organic compounds.24
(8) Brown, H. C.; Murray, K. J. Tetrahedron 1986, 42, 5497−5504.
(9) Brown, H. C.; Sharp, R. L. J. Am. Chem. Soc. 1966, 88, 5851−5854.
(10) Karlsson, S.; Hallberg, A.; Gronowitz, S. J. Organomet. Chem.
1991, 403, 133−144.
ASSOCIATED CONTENT
* Supporting Information
■
(11) For a recent overview, see: Keess, S.; Oestreich, M. Chem. Sci.
2017, 8, 4688−4695.
S
(12) (a) Chatterjee, I.; Oestreich, M. Angew. Chem., Int. Ed. 2015, 54,
1965−1968. (b) Chatterjee, I.; Qu, Z.-W.; Grimme, S.; Oestreich, M.
Angew. Chem., Int. Ed. 2015, 54, 12158−12162.
The Supporting Information is available free of charge on the
General procedures, experimental details, and character-
ization/spectral data for all compounds (PDF)
(13) For another example of an alkene transfer hydrogenation using a
cyclohexa-1,4-diene, see: Michelet, B.; Bour, C.; Gandon, V. Chem. -
Eur. J. 2014, 20, 14488−14492.
(14) For a comprehensive review of B(C6F5)3-catalyzed Si−H and
H−H bond activation, see: Oestreich, M.; Hermeke, J.; Mohr, J. Chem.
Soc. Rev. 2015, 44, 2202−2220.
AUTHOR INFORMATION
■
Corresponding Author
ORCID
(15) For a review of mainly FLP- but also B(C6F5)3-catalyzed
hydrogenation, see: Paradies, J. Angew. Chem., Int. Ed. 2014, 53, 3552−
3557 and references cited therein .
(16) Song, G.; Zheng, Z.; Wang, Y.; Yu, X. Org. Lett. 2016, 18, 6002−
Notes
6005.
(17) Keess, S.; Oestreich, M. Chem. - Eur. J. 2017, 23, 5925−5928.
(18) Chatterjee, I.; Oestreich, M. Org. Lett. 2016, 18, 2463−2466.
(19) Chatterjee, I.; Porwal, D.; Oestreich, M. Angew. Chem., Int. Ed.
2017, 56, 3389−3391.
(20) The Hammett constants for meta- and para-methoxy groups are
σm = 0.12 and σp = −0.27, respectively, see: Hansch, C.; Leo, A.; Taft, R.
W. Chem. Rev. 1991, 91, 165−195.
(21) The synthesis of the cyclopropyl-substituted compound was
therefore not attempted due to the low anticipated yield.
(22) Banerjee, S.; Vanka, K. ACS Catal. 2018, 8, 6163−6176.
(23) Hounjet, L. J.; Bannwarth, C.; Garon, C. N.; Caputo, C. B.;
Grimme, S.; Stephan, D. W. Angew. Chem., Int. Ed. 2013, 52, 7492−
7495.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by the Alexander von Humboldt
Foundation (Theodor Heuss Fellowship to J.C.L.W., 2017−
2018). M.O. is indebted to the Einstein Foundation Berlin for an
endowed professorship.
REFERENCES
■
(1) (a) Noyori, R. Angew. Chem., Int. Ed. 2002, 41, 2008−2022.
(b) Knowles, W. S. Angew. Chem., Int. Ed. 2002, 41, 1998−2007.
(2) Handbook of Homogeneous Hydrogenation; de Vries, J. G., Elsevier,
C. J., Eds.; Wiley-VCH: Weinheim, Germany, 2006.
(24) (a) Lloyd-Jones, G. C.; Munoz, M. P. J. Labelled Compd.
̃
Radiopharm. 2007, 50, 1072−1087. (b) Gant, T. G. J. Med. Chem. 2014,
57, 3595−3611. (c) Dickschat, J. S. Eur. J. Org. Chem. 2017, 4872−
4882. (d) Atzrodt, J.; Derdau, V.; Kerr, W. J.; Reid, M. Angew. Chem.,
Int. Ed. 2018, 57, 1758−1784.
(3) A Reaxys search for the deuteration of propene derivatives returns
346 individual reactions. For examples of the deuteration of α-
substituted styrenes, see: (a) Vidavsky, I.; Mandelbaum, A.; Tamiri, T.;
Zitrin, S. Org. Mass Spectrom. 1991, 26, 287−292. (b) Hou, D.-R.;
Reibenspies, J.; Colacot, T. J.; Burgess, K. Chem. - Eur. J. 2001, 7, 5391−
5400. (c) Ishibashi, Y.; Bessho, Y.; Yoshimura, M.; Tsukamoto, M.;
Kitamura, M. Angew. Chem., Int. Ed. 2005, 44, 7287−7290.
(d) Yoshimura, M.; Ishibashi, Y.; Miyata, K.; Bessho, Y.; Tsukamoto,
M.; Kitamura, M. Tetrahedron 2007, 63, 11399−11409. (e) Zhu, Y.;
̀
Fan, Y.; Burgess, K. J. Am. Chem. Soc. 2010, 132, 6249−6253. (f) Borras,
̀
́
C.; Biosca, M.; Pamies, O.; Dieguez, M. Organometallics 2015, 34,
5321−5334. (g) Yu, Y.-B.; Cheng, L.; Li, Y.-P.; Fu, Y.; Zhu, S.-F.; Zhou,
Q.-L. Chem. Commun. 2016, 52, 4812−4815. (h) Biosca, M.; Magre,
̀
́
M.; Coll, M.; Pamies, O.; Dieguez, M. Adv. Synth. Catal. 2017, 359,
2801−2814. (i) Liu, C.; Yuan, J.; Zhang, J.; Wang, Z.; Zhang, Z.; Zhang,
W. Org. Lett. 2018, 20, 108−111.
(4) Okuhara, T.; Kondo, T.; Tanaka, K.-I. J. Phys. Chem. 1977, 81,
808−809. The same authors also used MoS2 as catalyst and achieved a
1.5:1 selectivity in favor of the same product, see: Okuhara, T.; Tanaka,
K.-I. J. Chem. Soc., Chem. Commun. 1976, 199−200.
(5) Murahashi, S.-I.; Yano, T.; Hino, K.-i. Tetrahedron Lett. 1975,
4235−4238.
(6) The use of HD in the laboratory is hampered by both its high cost
($176/L at 96% isotopic purity, Cambridge Isotope Laboratories) and
D
Org. Lett. XXXX, XXX, XXX−XXX