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Study on 1,4-hydride shift triggered spirocyclization of arylidene imidazolones: substituent control on formation of indane or tetrahydrobenzazepine systems

Amir M. Al Mufti 1, 2
Amir M. Al Mufti
, 
Viktoria Алексеевна Ikonnikova 2
Viktoria Алексеевна Ikonnikova
, 
Alexander Yuryevich Smirnov 2, 3
Alexander Yuryevich Smirnov
, 
Vladislav Aleksandrovich Lushpa 2
Vladislav Aleksandrovich Lushpa
, 
Pavel Nikolaevich Solyev 4
Pavel Nikolaevich Solyev
, 
Mohamad Nurul Azmi 5
Mohamad Nurul Azmi
, 
Mikhail S. Baranov 2, 3
Mikhail S. Baranov
, 
Andrey Andreevich Mikhaylov 2, 3
Andrey Andreevich Mikhaylov
4 V. A. Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 119991 Moscow, Russian Federation
5 Natural Products and Synthesis Organic Research Laboratory (NPSO), School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden, Penang, Malaysia
10.71267/mencom.7550
Published 2025-01-24
Communication , Volume 35, Issue 1, 18-21
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Al Mufti A. M. et al. Study on 1,4-hydride shift triggered spirocyclization of arylidene imidazolones: substituent control on formation of indane or tetrahydrobenzazepine systems // Mendeleev Communications. 2025. Vol. 35. No. 1. pp. 18-21.
GOST all authors (up to 50) Copy
Al Mufti A. M., Ikonnikova V. А., Smirnov A. Y., Lushpa V. A., Solyev P. N., Azmi M. N., Baranov M. S., Mikhaylov A. A. Study on 1,4-hydride shift triggered spirocyclization of arylidene imidazolones: substituent control on formation of indane or tetrahydrobenzazepine systems // Mendeleev Communications. 2025. Vol. 35. No. 1. pp. 18-21.
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TY - JOUR
DO - 10.71267/mencom.7550
UR - https://mendcomm.colab.ws/publications/10.71267/mencom.7550
TI - Study on 1,4-hydride shift triggered spirocyclization of arylidene imidazolones: substituent control on formation of indane or tetrahydrobenzazepine systems
T2 - Mendeleev Communications
AU - Al Mufti, Amir M.
AU - Ikonnikova, Viktoria Алексеевна
AU - Smirnov, Alexander Yuryevich
AU - Lushpa, Vladislav Aleksandrovich
AU - Solyev, Pavel Nikolaevich
AU - Azmi, Mohamad Nurul
AU - Baranov, Mikhail S.
AU - Mikhaylov, Andrey Andreevich
PY - 2025
DA - 2025/01/24
PB - Mendeleev Communications
SP - 18-21
IS - 1
VL - 35
ER -
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@article{2025_Al Mufti,
author = {Amir M. Al Mufti and Viktoria Алексеевна Ikonnikova and Alexander Yuryevich Smirnov and Vladislav Aleksandrovich Lushpa and Pavel Nikolaevich Solyev and Mohamad Nurul Azmi and Mikhail S. Baranov and Andrey Andreevich Mikhaylov},
title = {Study on 1,4-hydride shift triggered spirocyclization of arylidene imidazolones: substituent control on formation of indane or tetrahydrobenzazepine systems},
journal = {Mendeleev Communications},
year = {2025},
volume = {35},
publisher = {Mendeleev Communications},
month = {Jan},
url = {https://mendcomm.colab.ws/publications/10.71267/mencom.7550},
number = {1},
pages = {18--21},
doi = {10.71267/mencom.7550}
}
MLA
Cite this
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Al Mufti, Amir M., et al. “Study on 1,4-hydride shift triggered spirocyclization of arylidene imidazolones: substituent control on formation of indane or tetrahydrobenzazepine systems.” Mendeleev Communications, vol. 35, no. 1, Jan. 2025, pp. 18-21. https://mendcomm.colab.ws/publications/10.71267/mencom.7550.

Keywords

benzazepine
hydride-shift triggered cyclization
imidazolones
indane
Lewis acid catalysis.
spiro compounds

Abstract

A rare process of 1,4-hydride or formal 1,6-hydride shift occurs in the (o-dialkylaminomethyl)arylidene imidazolones under the action of aluminum chloride. Only sterically hindered amino derivatives are able to enter the spirocyclization reaction, and the substituent would control this direction. Either five-membered indane in case of diisopropylamino derivatives, or seven-membered tetrahydrobenzazepines in case of dibenzylamino derivatives are formed in 46-84% yield.

Funders

Russian Science Foundation
20-73-10195

References

.
C–H Activation: Toward Sustainability and Applications
Dalton T., Faber T., Glorius F.
ACS Central Science, 2021
.
Synthesis and properties of 5-methylidene-3,5-dihydro-4H-imidazol-4-ones (microreview)
Baleeva N.S., Baranov M.S.
Chemistry of Heterocyclic Compounds, 2016
.
CH Bond Functionalization through Intramolecular Hydride Transfer
Haibach M.C., Seidel D.
Angewandte Chemie - International Edition, 2014
.
The redox-neutral approach to C-H functionalization.
Peng B., Maulide N.
Chemistry - A European Journal, 2013
.
Catalytic enantioselective intramolecular redox reactions: ring-fused tetrahydroquinolines.
Murarka S., Deb I., Zhang C., Seidel D.
Journal of the American Chemical Society, 2009
.
Imidazol-5-ones as a substrate for [1,5]-hydride shift triggered cyclization
Zaitseva E.R., Smirnov A.Y., Myasnyanko I.N., Mineev K.S., Sokolov A.I., Volkhina T.N., Mikhaylov A.A., Baleeva N.S., Baranov M.S.
New Journal of Chemistry, 2021
.
Redox economy in organic synthesis.
Burns N., Baran P., Hoffmann R.
Angewandte Chemie - International Edition, 2009
.
C–H activation
Rogge T., Kaplaneris N., Chatani N., Kim J., Chang S., Punji B., Schafer L.L., Musaev D.G., Wencel-Delord J., Roberts C.A., Sarpong R., Wilson Z.E., Brimble M.A., Johansson M.J., Ackermann L., et. al.
Nature Reviews Methods Primers, 2021
.
[1,5]-Hydride Shift-Cyclization versus C(sp2)-H Functionalization in the Knoevenagel-Cyclization Domino Reactions of 1,4- and 1,5-Benzoxazepines
Szalóki Vargáné D., Tóth L., Buglyó B., Kiss-Szikszai A., Mándi A., Mátyus P., Antus S., Chen Y., Li D., Tao L., Zhang H., Kurtán T.
Molecules, 2020
.
[1,5]-Hydride Shift Triggered N-Dealkylative Cyclization into 2-Oxo-1,2,3,4-tetrahydroquinoline-3-carboxylates via Boronate Complexes
Zaitseva E.R., Ivanov D.S., Smirnov A.Y., Mikhaylov A.A., Baleeva N.S., Baranov M.S.
Molecules, 2022
.
Chemo- and Regioselective Synthesis of Acyl-Cyclohexenes by a Tandem Acceptorless Dehydrogenation-[1,5]-Hydride Shift Cascade
Smith L.B., Armstrong R.J., Matheau-Raven D., Donohoe T.J.
Journal of the American Chemical Society, 2020
.
Convenient and Versatile Synthetic Protocol for Arylidene‐1 H ‐imidazol‐5(4 H )‐ones
Sokolov A.I., Myasnyanko I.N., Baleeva N.S., Baranov M.S.
ChemistrySelect, 2020
.
BF 3 Mediated [1,5]‐Hydride Shift Triggered Cyclization: Thioethers Join the Game
Zaitseva E.R., Smirnov A.Y., Timashev V.I., Malyshev V.I., Zhigileva E.A., Mikhaylov A.A., Medvedev M.G., Baleeva N.S., Baranov M.S.
European Journal of Organic Chemistry, 2022
.
tert-Amino effect: the Meth-Cohn and Reinhoudt reactions (Review)
Platonova A.Y., Glukhareva T.V., Zimovets O.A., Morzherin Y.Y.
Chemistry of Heterocyclic Compounds, 2013
.
Irbesartan
Gillis J.C., Markham A.
Drugs, 1997
.
Study on the scope of tert -amino effect: new extensions of type 2 reactions to bridged biaryls
Bottino P., Dunkel P., Schlich M., Galavotti L., Deme R., Regdon G., Bényei A., Pintye-Hódi K., Ronsisvalle G., Mátyus P.
Journal of Physical Organic Chemistry, 2012
.
The homologous tert-amino effect: a route to fused 2-benzazepine derivatives
Gorulya A.P., Tverdokhlebov A.V., Tolmachev A.A., Shishkin O.V., Shishkina S.V.
Tetrahedron, 2011
.
The Effect of Irbesartan on the Development of Diabetic Nephropathy in Patients with Type 2 Diabetes
Parving H., Lehnert H., Bröchner-Mortensen J., Gomis R., Andersen S., Arner P.
New England Journal of Medicine, 2001
.
Aromatization-driven cascade [1,5]-hydride transfer/cyclization for synthesis of spirochromanes
Cao L., Hu F., Dong J., Zhang X., Li S.
Organic Chemistry Frontiers, 2023
.
Photoinduced [1,5]-hydride shift triggered cyclization
Baleeva N.S., Smirnov A.Y., Zaitseva E.R., Ivanov D.S., Sokolov A.I., Mikhaylov A.A., Myasnyanko I.N., Baranov M.S.
New Journal of Chemistry, 2023
.
Divergent Synthesis of Multi-Substituted Phenanthrenes via Internal Redox Reaction/Ring Expansion Sequence
Koyama R., Anada M., Sueki S., Makino K., Kojima T., Kawasaki-Takasuka T., Mori K.
Chemical Communications, 2024
.
C(sp3)–H cyclizations of 2-(2-vinyl)phenoxy-tert-anilines
Dunkel P., Bogdán D., Deme R., Zimber Á., Ballayová V., Csizmadia E., Kontra B., Kalydi E., Bényei A., Mátyus P., Mucsi Z.
RSC Advances, 2024