I
P. H. Huy
Feature
Synthesis
1,2-Dichlorododecane (2u)
10145; Angew. Chem. 2016, 128, 10300. (b) Huy, P. H.; Filbrich, I.
Chem. Eur. J. 2018, 24, 7410. (c) Stach, T.; Dräger, J.; Huy, P. H.
Org. Lett. 2018, 20, 2980. (d) Motsch, S.; Schütz, C.; Huy, P. H.
Eur. J. Org. Chem. 2018, 4541.
According to the general procedure, PhthCl2 (480 L, 677 mg,
3.00 mmol, 1.5 equiv) was added by using a syringe pump within
30 min at 80 °C to a mixture of dodecanal (90% purity, 444 L,
369 mg, 2.00 mmol, 1.0 equiv) in DMF (2 M) and stirring was contin-
ued at 80 °C for 21 h. Work-up was performed according to protocol
III, which delivered the crude material (478 mg, 100%). 1H NMR analy-
sis verified a conversion of approximately ≥90%. Column chromato-
graphic purification on silica gel (6.1 g) with CH2Cl2/nHex 5:95 al-
lowed the isolation of the title compound as a brown oil (133 mg,
0.55 mmol, 28%) in a purity of circa 90% as judged by 1H NMR analy-
sis.
(5) (a) An, J.; Tang, X.; Moore, J.; Lewis, W.; Denton, R. M. Tetrahe-
dron 2013, 69, 8769. (b) Tang, X.; An, J.; Denton, R. M. Tetrahe-
dron Lett. 2014, 55, 799. (c) For a related catalytic deoxydichlori-
nation of epoxides, see: Denton, R. M.; Tang, X.; Przeslak, A. Org.
Lett. 2010, 10, 4678.
(6) Selected examples: (a) Okazoe, T.; Takai, K.; Utimoto, J. J. Am.
Chem. Soc. 1987, 109, 951. (b) Takeda, T.; Sasaki, R.; Fujiwara, T.
J. Org. Chem. 1998, 63, 7286. (c) Concellón, J. M.; Rodríguez-
Solla, H.; Díaz, P.; Llavona, R. J. Org. Chem. 2007, 72, 4396.
(d) Concellón, J. M.; Rodríguez-Solla, H.; de Amo, V.; Díaz, P. Syn-
thesis 2009, 2634.
(7) Selected examples: (a) Sengmany, S.; Léonel, E.; Paugam, J. P.;
Nédélec, J.-Y. Synthesis 2002, 533. (b) Oudeyer, S.; Léonel, E.;
Paugam, J. P.; Nédélec, J.-Y. Synthesis 2004, 389. (c) Oudeyer, S.;
Leonel, E.; Paugam, J. P.; Nédélec, J. Y. Tetrahedron 2014, 70, 919.
(d) Zhou, Y.-Y.; Uyeda, C. Angew. Chem. Int. Ed. 2016, 55, 3171.
(e) Durán-Peña, M. J.; Flores-Giubi, M. E.; Botubol-Ares, J. M.;
Harwood, L. M.; Collado, I. G.; Macías-Sánchez, A. J.; Hernández-
Galán, R. Org. Biomol. Chem. 2016, 14, 273.
(8) Selected examples: (a) Matsumoto, H.; Arai, T.; Takahashi, M.;
Ashizawa, T.; Nakano, T.; Nagai, Y. Bull. Chem. Soc. Jpn. 1983, 56,
3009. (b) Wey, H. G.; Butenschön, H. Chem. Ber. 1990, 123, 93.
(c) Qian, Y.; Li, G.; Zheng, X.; Huang, Y.-Z. Synlett 1991, 489.
(d) Barrero, A. F.; Herrador, M. M.; Quílez del Moral, J. F.;
Arteaga, P.; Akssira, M.; Hanbali, F. L.; Arteaga, J. F.; Diéguez, H.
R.; Sánchez, E. M. J. Org. Chem. 2007, 72, 2251. (e) Eisch, J. J.;
Qian, Y.; Rheingold, A. L. Eur. J. Inorg. Chem. 2007, 1576.
(9) Selected examples: (a) Giannerini, M.; Fañanas-Mastral, M.;
Feringa, B. L. J. Am. Chem. Soc. 2012, 134, 4108. (b) Li, H.; Müller,
D.; Guénée, L.; Alexakis, A. Org. Lett. 2012, 14, 5880. (c) Li, H.;
Grassi, G.; Gune, L.; Bürgi, T.; Alexakis, A. Chem. Eur. J. 2014, 20,
16694.
Rf = 0.80 + 0.72 (CH2Cl2/nHex, 5:95).
1H NMR (CDCl3, 400 MHz): = 5.74 (t, 3J = 6.2 Hz, 1 H, CHCl), 2.21–
2.17 (m, 2 H, CH2CHCl2), 1.57–1.51 (m, 2 H, CH2CH2CHCl2), 1.31–1.26
(m, 16 H, CH2), 0.88 (t, 3J = 6.8 Hz, 3 H, CH3).21
Funding Information
The author thanks the Deutsche Forschungsgemeinschaft (DFG) and
the Fonds der Chemischen Industrie (Liebig fellowship for P.H.) for
generous support.()
Acknowledgment
We would like to thank Rudolf Thomes (Saarland University) for mea-
suring HRMS.
Supporting Information
Supporting information for this article is available online at
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(10) Brzeskiewicz, J.; Loska, R.; Mąkosza, M. J. Org. Chem. 2018, 83,
8499.
References
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2019, 51, A–J