Mendeleev Commun., 2014, 24, 122–124
References
1
(a) M. Klussmann and D. Sureshkumar, Synthesis, 2011, 3, 353;
b) A. A. O. Sarhan and C. Bolm, Chem. Soc. Rev., 2009, 38, 2730.
OH
(
AlCl3
OH
OH
OCHO
OCHO
+
2 (a) S. Schenker, A. Zamfir, M. Freund and S. B. Tsogoeva, Eur. J. Org.
MeNO2
Chem., 2011, 2209; (b) J. M. Brunel, Chem. Rev., 2005, 105, 857;
(
(
c) Y. Chen, S. Yekta and A. K. Yudin, Chem. Rev., 2003, 103, 3155;
d) P. Kocovsky, S. Vyskocil and M. Smrcina, Chem. Rev., 2003, 103,
BINOL
6
3213; (e) E. E. Karslyan, A. I. Konovalov, A. O. Borissova, P. V. Petrovskii
and A. R. Kudinov, Mendeleev Commun., 2012, 22, 189.
AlCl3
3
(a) Methoden der Organischen Chemie, ed. H. G. Thomas, Thieme,
Stuttgart, 1976, vol.7/2b, p.1710; (b) I. B. Repinskaya and K. Yu.
Koltunov, Sib. Khim. Zh., 1993, 3, 73 (in Russian); (c) I. B. Repinskaya,
K. Yu. Koltunov, M. M. Shakirov, L. N. Shchegoleva and V. A. Koptyug,
Russ. J. Org. Chem., 1993, 29, 803 (Zh. Org. Khim., 1993, 29, 972) and
references cited therein.
MeNO2
Scheme 5
of aluminum halides.11 Therefore, participation of the latter as
possible alternative key intermediate is unfeasible.
4 (a) V. A. Koptyug and T. P. Andreeva, J. Org. Chem. USSR, 1971, 7, 2490
Zh. Org. Khim., 1971, 7, 2398); (b) K. Yu. Koltunov, I. B. Repinskaya,
M. M. Shakirov and L. N. Shchegoleva, Russ. J. Org. Chem., 1994, 30,
8 (Zh. Org. Khim., 1994, 30, 82); (c) K. Yu. Koltunov, A. N. Chernov,
(
Note also that instead of electrophilic reactions, the use
of AlCl /nitromethane medium leads to oxidative coupling of
3
8
1
(b),15
naphthols as a result of Scholl-type
reactions (Table 1,
G. K. S. Prakash and G. A. Olah, Chem. Pharm. Bull., 2012, 60, 722.
(a) K.Yu. Koltunov, E. N. Subbotina and I. B. Repinskaya, Russ. J. Org.
Chem., 1997, 33, 689 (Zh. Org. Khim., 1997, 33, 750); (b) K.Yu. Koltunov,
L. A. Ostashevskaya and I. B. Repinskaya, Russ. J. Org. Chem., 1998,
entry 6; Table 2, entries 14, 15). Remarkably, 2-naphthol gives
BINOL and its diformate 6 (Scheme 5). The latter is likely
produced through formylation of BINOL with an in situ formed
formic acid derivative, generated from nitromethane in the course
of the coupling reaction. Indeed, our attempts to directly formylate
BINOL with AlCl /nitromethane were unsuccessful. Close litera-
ture precedent exists for formylation of BINOL with such formic
acid derivative as N,N-diformylacetamide. Nevertheless, the
mechanism of the formation of 6, as well as synthetic significance
of this reaction is presently unclear and special investigation for
these matters is required.
5
‡
3
4, 1796 (Zh. Org. Khim., 1998, 34, 1870).
6
7
G.A. Olah and D.A. Klumpp, in Superelectrophiles and Their Chemistry,
Wiley, New York, 2008.
3
(a) I. B. Repinskaya, M. M. Shakirov, K.Yu. Koltunov andV.A. Koptyug,
J. Org. Chem. USSR, 1988, 24, 1719 (Zh. Org. Khim., 1988, 24, 1907);
(b) I. B. Repinskaya, K.Yu. Koltunov, M. M. Shakirov andV.A. Koptyug,
J. Org. Chem. USSR, 1992, 28, 785 (Zh. Org. Khim., 1992, 28, 1013).
K. Yu. Koltunov, Tetrahedron Lett., 2008, 49, 3891.
16
8
9
V. A. Ksenofontov, T. V. Vasina, Y. E. Zubarev and L. M. Kustov, React.
Kinet. Catal. Lett., 2003, 80, 329.
In conclusion, 1- and 2-naphthols undergo dimerization under
conditions that ensure their dicationic activation, in the presence
of an excess of aluminum halides. Dimerization of 1-naphthol is
not regioselective and gives complex mixture of isomers 3. In
contrast, 2-naphthol affords mainly dimer 4a, although the yield
is moderate because of the reaction reversibility. Despite the
modest initial results, both reactions exemplify a new approach
which can be of interest for the synthesis of non-symmetrically
functionalized binaphthyls. Evidently, in addition to the parent
naphthols, their derivatives may also exhibit analogous behavior.
The extension of this synthetic concept is now under way and
will be reported in due course.
1
0 (a) N. P. Buu-Hoi, H. Le Bihan and F. Binon, J. Org. Chem., 1951, 16,
85; (b) N. P. Buu-Hoi, H. Le Bihan, F. Binon and P. Rayet, J. Org.
Chem., 1950, 15, 1060.
11 V. A. Koptyug, T. P. Andreeva and V. I. Mamatyuk, J. Org. Chem. USSR,
970, 6, 1859 (Zh. Org. Khim., 1970, 6, 1848).
1
1
1
2 K. Yu. Koltunov, G. K. S. Prakash, G. Rasul and G. A. Olah, J. Org.
Chem., 2007, 72, 7394.
1
3 (a) G. A. Olah, G. K. S. Prakash, J. Sommer and A. Molnar, Superacid
nd
Chemistry, 2 edn., Wiley, 2009; (b) G. P. Smith, A. S. Dworkin, R. M.
Pagni and S. P. Zingg, J. Am. Chem. Soc., 1989, 111, 525; (c) G. P. Smith,
A. S. Dworkin, R. M. Pagni and S. P. Zingg, J. Am. Chem. Soc., 1989,
1
11, 5075.
1
1
4 K. Yu. Koltunov, G. K. S. Prakash, G. Rasul and G. A. Olah, J. Org.
Chem., 2002, 67, 4330.
5 A. J. Fatiadi, J. Res. Nat. Bur. Stand., Sect. A, 1968, 72A, 39, and
references cited therein.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2014.02.020.
16 (a) G. Ziegler and W. Kantlehner, Z. Naturforsch. B, 2001, 56, 1172;
(b) W. Kantlehner, Eur. J. Org. Chem., 2003, 2530.
‡
The diester 6 is a known compound;16(a) spectroscopic data are listed
1
here as an update. H NMR (500 MHz, CDCl ) d: 7.22 (d, 1H, J 8.5 Hz),
3
7
(
.38 (t, 1H, J 8.5 Hz), 7.54 (t, 1H, J 8.2 Hz), 7.80 (d, 1H, J 8.2 Hz), 7.81
d, 1H, J 8.9 Hz), 7.97 (d, 1H, J 8.9 Hz), 9.18 (s, 1H). 13C NMR (125 MHz,
CDCl ) d: 117.7, 119.1, 120.3, 123.8, 127.7, 129.3, 132.1, 132.8, 150.1,
3
+
1
57.9. GC-MS, m/z: 342 [M] .
Received: 5th September 2013; Com. 13/4196
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