Home / Articles / Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation

Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation

Irina A Borisova 1
Irina A Borisova
, 
Konstantin Vladislavovich Potapov 1
Konstantin Vladislavovich Potapov
, 
Anna D Maximova 1
Anna D Maximova
, 
Maxim Alexandrovich Novikov 1
Maxim Alexandrovich Novikov
, 
Roman Aleksandrovich Novikov 1
Roman Aleksandrovich Novikov
, 
10.71267/mencom.7966
Published 4 June 2026 , received 7 November 2025
Communication , Volume 36, Issue 4, 463-465
0
Share
Cite this
GOST
 | 
Cite this
GOST
Copy cite
Borisova I. A. et al. Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation // Mendeleev Communications. 2026. Vol. 36. No. 4. pp. 463-465.
GOST all authors (up to 50)
Copy cite
Borisova I. A., Potapov K. V., Maximova A. D., Novikov M. A., Novikov R. A., Tomilov Y. V. Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation // Mendeleev Communications. 2026. Vol. 36. No. 4. pp. 463-465.
RIS
 | 
Cite this
RIS
Copy cite
TY - JOUR
DO - 10.71267/mencom.7966
UR - https://mendcomm.colab.ws/publications/10.71267/mencom.7966
TI - Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation
T2 - Mendeleev Communications
AU - Borisova, Irina A
AU - Potapov, Konstantin Vladislavovich
AU - Maximova, Anna D
AU - Novikov, Maxim Alexandrovich
AU - Novikov, Roman Aleksandrovich
AU - Tomilov, Yury Vasil'evich
PY - 2026
DA - 2026/06/04
PB - Mendeleev Communications
SP - 463-465
IS - 4
VL - 36
ER -
BibTex
 | 
Cite this
BibTex (up to 50 authors)
Copy cite
@article{2026_Borisova,
author = {Irina A Borisova and Konstantin Vladislavovich Potapov and Anna D Maximova and Maxim Alexandrovich Novikov and Roman Aleksandrovich Novikov and Yury Vasil'evich Tomilov},
title = {Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation},
journal = {Mendeleev Communications},
year = {2026},
volume = {36},
publisher = {Mendeleev Communications},
month = {Jun},
url = {https://mendcomm.colab.ws/publications/10.71267/mencom.7966},
number = {4},
pages = {463--465},
doi = {10.71267/mencom.7966}
}
MLA
Cite this
MLA
Copy cite
Borisova, Irina A., et al. “Lewis acid mediated rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5): an experimental evidence of stepwise 1,2-zwitter-ion formation.” Mendeleev Communications, vol. 36, no. 4, Jun. 2026, pp. 463-465. https://mendcomm.colab.ws/publications/10.71267/mencom.7966.
Views / Visits
29 / 29

Keywords

1,2-zwitter-ions
carbocation rearrangements
donor–acceptor cyclopropanes
gallium chloride
ring expansion
spiroalkanes
titanium chloride

Abstract

The ability of TiCl4 and GaCl3 effectively mediate rearrangements of spiro[2.n]alkane-1,1-dicarboxylates (n = 2–5) to (alkylidene)malonates was shown, the mechanism involving formation of 1,2-zwitter-ion species. In the case of TiCl4, stepwise (alkylidene)malonate formation pathway was postulated that involves preliminary chloride-mediated cyclopropane ring-opening followed by 1,2-H and 1,2-alkyl migrations.

Funders

Russian Science Foundation
25-13-00574

References

1.
A New Golden Age for Donor-Acceptor Cyclopropanes
Schneider T.F., Kaschel J., Werz D.B.
Angewandte Chemie - International Edition, 2014
2.
Intramolecular donor–acceptor cyclopropane ring-opening cyclizations
Cavitt M.A., Phun L.H., France S.
Chemical Society Reviews, 2014
3.
Carbocycles from donor–acceptor cyclopropanes
Grover H.K., Emmett M.R., Kerr M.A.
Organic and Biomolecular Chemistry, 2015
4.
Ring Opening of Donor–Acceptor Cyclopropanes with N-Nucleo­philes
Budynina E., Ivanov K., Sorokin I., Melnikov M.
Synthesis, 2017
5.
Donor‐Acceptor Cyclopropanes in the Synthesis of Carbocycles
Ivanova O.A., Trushkov I.V.
Chemical Record, 2019
7.
Mel’nikov M.Y., Budynina E.M., Ivanova O.A., Trushkov I.V.
Mendeleev Communications, 2011
8.
A New Type of Donor-Acceptor Cyclopropane Reactivity: The Generation of Formal 1,2- and 1,4-Dipoles
Novikov R.A., Tarasova A.V., Korolev V.A., Timofeev V.P., Tomilov Y.V.
Angewandte Chemie - International Edition, 2014
9.
GaCl3 -Mediated Reactions of Donor-Acceptor Cyclopropanes with Aromatic Aldehydes
Borisov D.D., Novikov R.A., Tomilov Y.V.
Angewandte Chemie - International Edition, 2016
10.
[4 + 2] Annulation of Donor–Acceptor Cyclopropanes with Acetylenes Using 1,2-Zwitterionic Reactivity
Novikov R.A., Tarasova A.V., Denisov D.A., Borisov D.D., Korolev V.A., Timofeev V.P., Tomilov Y.V.
Journal of Organic Chemistry, 2017
11.
Denisov Dmitry Alekseevich, Borisov Denis Dmitrievich, Potapov Konstantin Vladislavovich, Novikov Roman Aleksandrovich, Tomilov Yury Vasil'evich
Mendeleev Communications, 2019
13.
Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C‐C Cleavage Strategy
Nguyen T.V., Brownsey D.K., Bossonnet A., Wodrich M.D., Waser J.
Angewandte Chemie - International Edition, 2024
14.
Photocatalyzed [2σ + 2σ] and [2σ + 2π] Cycloadditions for the Synthesis of Bicyclo[3.1.1]heptanes and 5- or 6-Membered Carbocycles
Nguyen T.V., Bossonnet A., Wodrich M.D., Waser J.
Journal of the American Chemical Society, 2023
15.
SmI2-Catalyzed Intermolecular Coupling of Cyclopropyl Ketones and Alkynes: A Link between Ketone Conformation and Reactivity
Agasti S., Beattie N.A., McDouall J.J., Procter D.J.
Journal of the American Chemical Society, 2021
17.
Synthesis of Enantiopure Indolizinones by Cascade Ring Enlargements of 4‘-Chlorospiro[cyclopropane-1,5‘-isoxazolidines]
Revuelta J., Cicchi S., Faggi C., Kozhushkov S.I., de Meijere A., Brandi A.
Journal of Organic Chemistry, 2006
19.
Why a cyclopropyl group is good at stabilizing a cation but poor at transmitting substituent effects
Wilcox C.F., Loew L.M., Hoffmann R.
Journal of the American Chemical Society, 1973
21.
Complexes of Donor–Acceptor Cyclopropanes with Tin, Titanium, and Gallium Chlorides — Mechanism Studies
Novikov R.A., Balakirev D.O., Timofeev V.P., Tomilov Y.V.
Organometallics, 2012