4
Tetrahedron Letters
3.88 (m, 2H), 3.96 (m, 2H), 5.01 (t, J = 4.6 Hz, 1H); 13C NMR
Org. Synth. Coll. Vol. 1990, 7, 356–359; (c) Golding, B. T.; Hall,
D. R.; Sakrikar, S. J. Chem. Soc. Perkin Trans. 1 1973, 1214–
1220.
(126 MHz, CDCl3) 27.14, 36.97, 64.78 (2C), 102.34.
14. Our papers for bromination methodology: (a) Manabe, Y.;
Kitawaki, Y.; Nagasaki, M.; Fukase,K.; Matsubara, H.; Hino, Y.;
Fukuyama, T.; Ryu, I. Chem. Eur. J. 2014, 20, 12750–12753; (b)
Matsubara, H.; Tsukida, M.; Ishihara, D.; Kuniyoshi, K.; Ryu, I.
Synlett 2010, 2014–2018; (c) Ryu, I.; H.; Matsubara, Nakamura,
H.; Curran, D. P. Chem. Rec. 2008, 8, 351–363; (d) Rahman, M.
T.; Kamata, N.; Matsubara, H.; Ryu, I. Synlett 2005, 2664–2666;
(e) Nakamura, H.; Usui, T.; Kuroda, H.; Ryu, I.; Matsubara, H.;
Yasuda, S.; Curran, D. P. Org. Lett. 2003, 5, 1167–1169; (f) Ryu,
I.; Matsubara, H.; Yasuda, S.; Nakamura, H.; Curran, D. P. J. Am.
Chem. Soc. 2002, 124, 12946–12947.
References and notes
1.
Reviews for NBS (N-bromosuccinimide): (a) Virgil, S. C. In
Encyclopedia of Reagents for Organic Synthesis, 2nd Ed. Paquett,
L. A.; Crich, D.; Fuchs, P. L.; Molander, G. A. Ed.; Wiley,
Chichester, 2009; Vol. 3, pp 1657–1667; (b) (a) Fieser, L. F;
Fieser, M. Reagents for Organic Synthesis, Vol. 1; Wiely: New
York, 1967: pp 78–80.
2.
3.
Work for NBS: (a) Hashimoto, H.; Kawa, M.; Saito, Y.; Date, T.;
Horito, S.; Yoshimura, J. Tetrahedron Lett. 1987, 28, 3505–3508;
(b) Yang, X.; Wu, J.; Mao, X.; Jamison, T. F.; Hatton, T. A.
Chem. Commun. 2014, 50, 3245–3248; (c) Shinde M. H.;
Kshirsagar, U. Org. Biomol. Chem. 2016, 14, 858–861
Reviews for BDMS (bromodimethylsulfonium bromide): (a) Das,
B.; Krishnaiah, M. In Encyclopedia of Reagents for Organic
Synthesis, 2nd Ed. Paquett, L. A.; Crich, D.; Fuchs, P. L.;
Molander, G. A. Ed.; Wiley, Chichester, 2009; Vol. 3, pp 1573–
1575; (b) Choudhury, L. H.; Parvin, T.; Khan, A. T. Tetrahedron
2009, 65, 9513–9526.
15. Yasuda, H.; Uenoyama, Y.; Nobuta, O.; Kobayashi, S.; Ryu, I.
Tetrahedron Lett. 2008, 49, 367–370.
16. Watanabe, K.; Yamagiwa, N.; Torisawa, Y. Org. Process Res.
Dev. 2007, 11, 251–258.
17. Van Cleave et al. reported that 1,4-dioxane reacts slowly with
anhydrous HBr at room temperature to afford 2,2'-dibromodiethyl
ether (Van Cleave, A. B.; Blake, R. I. Can. J. Chem. 1951, 29,
785–789). We confirmed that no 1,4-dioxane decomposition
products were observed by GC analysis after treatment with HBr
gas at 25 °C for 30 min. They also reported that the HBr/1,4-
dioxane solution, initially at 0.821 M in HBr, was determined to
be 0.301 M after 30 days at 25°C. In other words, the HBr level
decreased to 37% of the initial concentration over that period,
which does not contradict our HBr retention tests results.
18. Although the outcomes in Table 3 are counterintuitive, it is known
that anti-Markovnikov addition of HBr takes place without
peroxide9a,23 Interestingly, the origin of this "abnormal" addition is
still unclear.23,24 To suppress the formation of radical species, we
carried out hydrobromination of tetradecene (2a) with HBr/1,4-
dioxane solution (1c) in the presence of 10 mol% of a radical
inhibitor, BHT, under N2.24 However, the anti-Markovnikov-type
product, 1-bromotetradecane (3a), was still obtained in 90% yield.
19. Solvents can influence regioselectivity in the hydrobromination of
alkenes with HBr.23 We also demonstrated that the
4.
Recent work for BDMS: (a) Yadav, L. D. S.; Patel, R.; Srivastava,
V. P. Synthesis 2010, 1771–1776; (b) Khan, A. T.; Ali, M. A.;
Goswami, P.; Choudhury, L. H. J. Org. Chem. 2006, 71, 8961–
8963; (c) Karki, M.; Magolan, J. J. Org. Chem. 2015, 80, 3701–
3707; (d) Choudhury, L. H.; Parvin, T.; Khan, A. Tetrahedron
2009, 65, 9513–9526.
5.
6.
A review for DBI (1,3-dibromoisocyanuric acid): Virgil, S. C. In
Encyclopedia of Reagents for Organic Synthesis, 2nd Ed. Paquett,
L. A.; Crich, D.; Fuchs, P. L.; Molander, G. A. Ed.; Wiley,
Chichester, 2009; Vol. 4, pp 3127–3128.
Work for DBI: (a) Gottardi, W. Monatsch. Chem. 1968, 99, 815–
822; (b) Kogon, A. A.; Bochkariov, D. E.; Baskunov, B. P.;
Cheprakov, A. V. Liebigs Ann. Chem. 1992, 879–881; (c) Chen,
J.; Shi, M.-M.; Hu, X.-L.; Wang, M.; Chen, H.-Z. Polymer 2010,
51, 2897–2902.
hydrobromination of 2a with 1c in CH2Cl2 or 1,2-dichloroethane
afforded the Markovnikov product, 2-bromotetradecane (4a), in
95% or 90% yields, together with a trace amount (< 1%) or 10%
of the anti-Markovnikov product 3a, respectively.
7.
8.
A review for HBr: Breton G. W.; Kropp, P. J. In Encyclopedia of
Reagents for Organic Synthesis, 2nd Ed. Paquett, L. A.; Crich, D.;
Fuchs, P. L.; Molander, G. A. Ed.; Wiley, Chichester, 2009; Vol.
7, pp 5404–5406.
Reviews for hydrobromination using HBr: (a) Li, W.; Zhang, J. In
Comprehensive Organic Synthesis 2nd Ed.; Knochel, P.;
Molander, G. A. Ed.; Elsevier, Amsterdam, 2014; Vol. 4, pp 352–
356. (b) Larock, R. C.; Leong, W. W. In Comprehensive Organic
Synthesis; Trost B. M.; Fleming, I., Ed.; Pergamon Press: Oxford,
1991; Vol. 4, pp 269–327; (c) Stacey, F.W.; Harris, Jr., J. F. Org.
React. 1963, 13, 154–164.
For example, (a) Smith, M. B. In March’s Advanced Organic
Chemistry, Reactions, Mechanisms, and Structure, 7th Ed.; Wiley,
New Jersey, 2013, pp 883–884; (b) Isenberg, N.; Grdinic, M. J.
Chem. Educ. 1969, 46, 601–605; (c) Galli, M.; Fletcher, C. J.; del
Pozo, M.; Goldup, S. M. Org. Biomol. Chem. 2016, 14, 5622–
5626.
20. Bell, R. P. The Proton in Chemistry, 2nd Ed; Cornell University
Press, Ithaca, NY, 1973.
21. (a) Buechi, G.; Wuest, H. J. Org. Chem. 1969, 34, 1122–1123; (b)
Stowell, J. C.; Keith, D. R.; King, B. T. Org. Synth. Coll. Vol.
1990, 7, 59–63.
22. To examine the scalability of reactions with HBr solution 1c, we
have prepared 2-(2-bromoethyl)-1,3-dioxolane (10a) from 1.68 g
(30 mmol) of acrolein, obtaining 5.18 g (95%) of the desired
product. This demonstrates that preparation of the dioxolane on
even a 5-g scale can be successfully performed using 1c.
23. For example, (a) Sherrili, M.; Mayer, K. E.; Walter, G. F. J. Am.
Chem. Soc. 1934, 56, 926–930; (b) Walker, J.; Lumsden, J. S. J.
Chem. Soc. 1901, 79, 1191–1197; (c) Linstead, R. P.; Rydon, H.
N. Nature 1933, 132, 643–643.
9.
10. For example, (a) Larock R. C Comprehensive Organic
Transformations 2nd Ed.; Wiely-VCH: New York, 1999; p 693;
(b) Reid, E. E.; Ruhoff, J. R.; Burnett, R. E. Org. Synth. Coll. Vol.
1943, 2, 246–248; (c) Kamm, O.; Marvel, C. S. Org. Synth. Coll.
Vol. 1941, 1, 25–35; (d) Anzi, A. E.; Benazza, M.; Fréchou, C.;
Demailly, G. Tetrahedron Lett. 1993, 34, 3741–3744.
11. Preparation of HBr gas in laboratories, see: (a) Fieser, L. F; Fieser,
M. Reagents for Organic Synthesis, Vol. 1; Wiely: New
York,1967: pp 453–454; (b) Tietze, L. F.; Eicher, T. In Reactions
and Syntheses; University Science Books, Mill Valley, CA, 1988;
pp 469–470.
12. (a) Fieser, L. F; Fieser, M. Reagents for Organic Synthesis, Vol. 1;
Wiely: New York,1967: pp 450–452; (b) Mills J. E. In
Encyclopaedia of Reagents for Organic Synthesis, 2nd Ed.
Paquett, L. A.; Crich, D.; Fuchs, P. L.; Molander, G. A. Ed.;
Wiley, Chichester, 2009; Vol. 7, pp 5394–5399.
24. Sergeev, G. B.; Stepanov, N. F.; Leenson, I. A.; Smirnov, V. V.;
Pupyshev, V. I.; Tyurina, L. A.; Mashyanov, M. N. Tetrahedron
1982, 38, 2585–2589.
Supplementary Material
All compounds prepared in this study are known compounds.
1
Supplementary data (Tables S1 and S2, Experimental details, H
and 13C NMR data of compounds prepared in this study) can be
found in the online version, at http://
13. (a) Fieser, L. F; Fieser, M. Reagents for Organic Synthesis, Vol. 1;
Wiely: New York, 1967; p 452; (b) Ellis, M. K.; Golding, B. T.