8 of 10
SEMENOK ET AL.
[3] E. T. Satumov, J. J. Medvedev, D. I. Nilov, M. A. Sandzhieva, I.
A. Boyarskaya, N. A. Nikolaev, A. V. Vasilyev, Tetrahedron
2016, 72, 4835.
4 | MATERIALS AND METHODS
Synthesis of diazo compounds 1‐4 was previously
described in several publications.[12,22–24] Regioisomeric
products of migration can be distinguished by position
[4] C. Zhai, D. Xing, C. Jing, J. Zhou, C. Wang, D. Wang, W. Hu,
Org. Lett. 2014, 16, 2934.
1
[5] J. J. Medvedev, D. V. Semenok, X. V. Azarova, L. L. Rodina, V.
and intensity of H NMR signals of aryl protons, e.g., by
A. Nikolaev, Synthesis 2016, 48, 4525.
comparison of downfield doublets of o‐protons in
p‐XPh‐ (X = Cl, F, SOnMe), which can be compared
directly for both regioisomers. 1H and 13C NMR
spectra of different regioisomers were previously pub-
lished.[5,22–24] Single‐crystal X‐ray diffraction (XRD) was
used in some cases[25] to determine structure of the major
products of migration.
[6] (a) M. Regitz, G. Maas, Diazo Compounds, Properties and Syn-
thesis, Academic Press, New York 1986. (b) H. Dahn, H. Gold,
Helv. Chim. Acta 1963, 46, 983.
[7] A. B. Smith III, R. K. Dieter, Tetrahedron 1981, 37, 2407.
[8] V. Rendina, J. Kingsbury, J. Org. Chem. 2012, 77(2), 1181.
[9] H. C. Brown, Y. Okamoto, J. Am. Chem. Soc. 1958, 80, 4979.
[10] G. A. Olah, G. K. S. Prakash, A. Molnar, J. Sommer, Superacid
chemistry, 2nd ed. John Wiley & Sons, Inc., U.S. 2009,36‐37.
All decomposition reactions were carried out in sol-
vents purified and dried according to common methods.
Monitoring of the reactions was implemented by thin‐
layer chromatography (TLC) on aluminum silica gel
[11] David R. Lide (ed.), CRC Handbook of Chemistry and Physics,
Int. version, 2005.
1
F254 plates (Merck Co). Н, 13C, and 19F NMR spectra,
[12] (a) L. L. Rodina, Y. Medvedev Yu, P. N. Moroz, V. A. Nikolaev,
Russian Journal of Organic Chemistry 2012, 48(4), 602. (b) L.
Rodina, J. Medvedev, O. Galkina, V. Nikolaev, European Jour-
nal of Organic Chemistry 2014, 14, 2993. (c) S. A. Malashikhin,
L. L. Rodina, V. A. Nikolaev, L. Anthony, H. Heinz, Helv.
Chim. Acta 2008, 91, 1662.
recorded on a Bruker 400 AVANCE or Bruker 300
NMR spectrometers in CDCl3 or acetone‐d6, were used
for identification of starting materials and decomposition
products. The electrospray high‐resolution (HR) mass
spectra were recorded on the MaXis (Bruker Daltonik
GmbH).
[13] M. Ernzerhof, J. P. Perdew, J. Chem. Phys. 1998, 109. C. Adamo,
V. Barone, J. Chem. Phys. 1999, 110, 6158. M. Ernzerhof, G. E.
Scuseria, J. Chem. Phys. 1999, 110, 5029.
[14] A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
ACKNOWLEDGMENTS
[15] G. A. Petersson, A. Bennett, T. G. Tensfeldt, M. A. Al‐
Laham, W. A. Shirley, J. Mantzaris, J. Chem. Phys. 1988, 89,
2193. G. A. Petersson, M. A. Al‐Laham, J. Chem. Phys. 1991,
94, 6081.
The authors express their gratitude to the SPbSU resource
centers: “Center for Magnetic Resonance,” “Computer
Center SPbU,” “Cryogenic Department,” “Interdisciplin-
ary Resource Centre for Nanotechnology,” “Centre for
X‐ray Diffraction Studies,” and “Center for Optical and
Laser Research.” Thanks to V. Pavlovsky for calcula-
tions of dielectric constants of solvents at different tem-
peratures and Peter Sherin for improving the readability
of the manuscript. D.S. and J.M. express their gratitude
to the Russian Foundation for Basic Research, grant
mol_a no. 16‐33‐00059. J.M. is also grateful to Saint‐
Petersburg State University for financial support for
(event 6, 2017).
[16] Gaussian 09, Revision A.02, M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G.
Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M.
Caricato, A. Marenich, J. Bloino, B. G. Janesko, R. Gomperts,
B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J.
L. Sonnenberg, D. Williams‐Young, F. Ding, F. Lipparini, F.
Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D.
Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W.
Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T.
Vreven, K. Throssell, J. A. Montgomery, Jr., J. E. Peralta, F.
Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V.
N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi,
M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W.
Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B.
Foresman, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2016.
ORCID
[17] J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 2005, 105, 2999.
REFERENCES
[18] B.P. Nikol'sky, Handbook Chemist, Rus. Ed., Book 3, p. 958,
[1] T. Hashimoto, K. Maruoka, Bull. Chem. Soc. Jpn. 2013, 86,
Moscow, 1965.
1217.
[19] A. Gioiello, F. Venturoni, M. Marinozzi, B. Natalini, R.
Pellicciari, J. Org. Chem. 2011, 76, 7431.
[2] (a) A. N. Kazakova, A. V. Vasilyev, Russian Journal of Organic
Chemistry 2017, 53, 485. (b) M. Allard, J. Levisalles, J. M.
Sommer, Journal of the Chemical Society [Section] D: Chemical
Communications 1969, 0, 1515.
[20] J. Engberts, B. Zwanenburg, Tetrahedron 1968, 24, 1737.
[21] M. G. Evans, M. Polanyi, Trans. Faraday Soc. 1935, 1935(31),
875.