Mendeleev Commun., 2018, 28, 577–578
R
OH
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2018.11.003.
i
OH
Me
+
+
R
HO
OH
R
R
4
4
a, 28%
b, 30%
5a, 31%
5b, 30%
6a, 31%
6b, 32%
B
References
OH
3a,b
R
1 (a) L. I. Khusainova, L. O. Khafizova, T.V. Tyumkina and U. M. Dzhemilev,
Russ. J. Gen. Chem., 2016, 86, 1438 (Zh. Obshch. Khim., 2016, 86, 1046);
a R = n-C6H13
b R = n-C8H17
ii
B
O
B
(b) L. I. Khusainova, L. O. Khafizova, T.V. Tyumkina and U. M. Dzhemilev,
Russ. J. Org. Chem., 2015, 51, 1516 (Zh. Org. Khim., 2015, 51, 1551).
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H. Wiltz, L. T. Zane and R. Pollak, J. Am. Acad. Dermatol., 2015, 73, 62;
R
7
7
a, 72%
b, 61%
(
b)A. K. Gupta and D. Daigle, Expert Rev. Anti-Infect. Ther., 2014, 12, 735;
–
Scheme 3 Reagents and conditions: i, H O , OH , 0°C; ii, MgSO , ~20°C,
neat, 24 h.
(c) S. J. Baker, Y.-K. Zhang, T. Akama, A. Lau, H. Zhou, V. Hernandez,
W. Mao, M. R. K. Alley, V. Sanders and J. J. Plattner, J. Med. Chem., 2006,
2
2
4
4
9, 4447; (d) A. Paramore and S. Frantz, Nat. Rev. Drug Discov., 2003, 2,
6
11; (e)A. S. Ivanov,A.A. Zhalnina and S. V. Shishkov, Tetrehedron, 2009,
alkanols 5a,b and 6a,b have been obtained in 82–85% total yield
5
65, 7105; ( f ) J. Adams, M. Behnke, S. Chen, A. A. Cruickshank, L. R. Dick,
L. Grenier, J. M. Klunder,Y.-T. Ma, L. Plamondon and R. L. Stein, Bioorg.
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M. Meewan, M. Mohan, W. Mao, F. L. Rock, H. Sexton, A. Sheoran,
Y. Zhang, Y.-K. Zhang, Y. Zhou, J. A. Nieman, M. R. Anugula, E. M.
Keramane, K. Savariraj, D. S. Reddy, R. Sharma, R. Subedi, R. Singh,
A. O’Leary, N. L. Simon, P. L. De Marsh, S. Mushtaq, M. Warner, D. M.
Livermore, M. R. K.Alley and J. J. Plattner, Antimicrob. Agents Chemother.,
(Scheme 3), their spectra were close to the published ones.
We have found that boriranols 3a,b at room temperature are
partially converted into the corresponding diboroxanes 7a,b (see
Scheme 3). While storing compounds 3a,b in the presence of
anhydrous MgSO for 24 h, almost complete transformation into
4
‡
11
anhydrides 7a,b occurs. In the B NMR spectra of the latter, the
signals of boron atom at ~18 ppm are shifted upfield compared to
the parent boriranols 3a,b (d ~32 ppm). Molecular weight of
B
2
013, 57, 1394; (h) E. Sonoiki, C. L. Ng, M. C. S. Lee, D. Guo, Y.-K.
6
dibroxanes 7a,b was evaluated by the cryoscopy method since
Zhang, Y. Zhou, M. R. K. Alley, V. Ahyong, L. M. Sanz, M. J. Lafuente-
Monasterio, C. Dong, P. G. Schupp, J. Gut, J. Legac, R. A. Cooper, F.-J.
Gamo, J. DeRisi, Y. R. Freund, D. A. Fidock and P. J. Rosenthal, Nat.
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Chem., 2015, 58, 3682; (k) Z. J. Lesnikowski, Expert Opin. Drug Discov.,
they are easily destroyed under the conditions of the mass spectro-
metric analysis.
In summary, we have elaborated a new one-pot synthesis of
previously undescribed 2-alkylboriran-1-ols in 90–92% yield. The
method is based on the use of the catalytic cycloboration reaction
1
of α-olefins with complexes of boron trihalides (BF ·THF and
3
BCl ·SMe ) in the presence of metallic Mg (halogen ion acceptor)
3
2
and Cp TiCl catalyst leading to 1-fluoro- and 1-chloroboriranes,
2
2
2016, 11, 569; (l) H. S. Ban and H. Nakamura, Chem. Rec., 2015, 15, 616;
which are further subjected to hydrolysis.
(m) S. J. Baker, C. Z. Ding, T. Akama,Y.-K. Zhang, V. Hernandes andY. Xia,
We believe that the developed approach has a great synthetic
potential for the production of diverse boriran-1-ols, which can
serve as precursors in the creation of modern selective medicines.
Future Med. Chem., 2009, 1, 1275.
(a) A. J. Ashe III, W. Klein and R. Rousseau, Organometallics, 1993, 12,
3
3
1
225; (b) H. C. Brown and N. Ravindran, J. Am. Chem. Soc., 1976, 98,
798.
This work was supported by the Russian Science Foundation
project no. 17-73-10124).
4 L. I. Khusainova, L. O. Khafizova, T. V. Tyumkina, K. S. Ryazanov and
U. M. Dzhemilev, J. Organomet. Chem., 2017, 832, 12.
(
5
(a) P. Shao, L. Shen and S.Ye, Chin. J. Chem., 2012, 30, 2688; (b) I. Prat,
D. Font, A. Company, K. Junge, X. Ribas, M. Beller and M. Costas, Adv.
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‡
Diboroxanes 7a,b. A solution of boriranol 3a,b (0.5 mmol) in CDCl3
(
0.5 ml) was treated with anhydrous MgSO (50 mg) for 24 h. Yields of
4
compounds 7a,b were determined from the integrated intensity of the
signals of boron atoms in the 11B NMR spectrum.
1
1
,1'-Oxybis(2-hexylborirane) 7a. Yield 72%. H NMR, d: 0.90 (t, 6H,
(
f) E. Fernández-Mateos, B. Maciá and M. Yus, Adv. Synth. Catal., 2013,
13
2
2
Me, J 6.2 Hz), 1.21–1.50 (m, 16H, 8CH2). C NMR, d: 14.07, 22.63,
355, 1249.
9.24, 29.31, 31.80. 11B NMR, d: 18.62. In the H and C spectra signals
1
13
6 (a) E. L. Scau, J. C. Artur, Jr. and H. Wakeham, Technique of Organic
2
rd
of protons and carbon atoms directly attached to the boron atom [C H,
Chemistry, 3 edn., ed. A. Weissberger, Interscience, New York, 1959,
2'
3
3'
4
4'
C H, C H , C H (cycle)] and C H , C H were not detected.
vol. 1, p. 342; (b) J. J. Alexander and M. J. Steffel, Chemistry in the
Laboratory, Harcourt Brace Jovanovich, Inc., New York, 1976, p. 143.
2
2
2
2
1
1
,1'-Oxybis(2-octylborirane) 7b. Yield 61%. H NMR, d: 0.89 (t, 6H,
13
2
2
Me, J 6.8 Hz), 1.20–1.50 (m, 24H, 12CH ). C NMR, d: 14.09, 22.67,
2
9.34, 29.49, 29.61, 29.64, 31.91. 11B NMR, d: 18.34. In the H and
1
13
C
spectra signals of protons and carbon atoms directly attached to the boron
2
2'
3
3'
4
4'
atom [C H, C H, C H , C H (cycle)] and C H , C H were not detected.
Received: 7th May 2018; Com. 18/5569
2
2
2
2
–
578 –