Synthesis of a Chiral C-2-Symmetric Sterically Hindered Pyrrolidine Nitroxide Radical via Combined Iterative Nucleophilic Additions and Intramolecular 1,3-Dipolar Cycloadditions to Cyclic Nitrones

Synthesis of a Chiral C-2-Symmetric Sterically Hindered Pyrrolidine Nitroxide Radical via Combined Iterative Nucleophilic Additions and Intramolecular 1,3-Dipolar Cycloadditions to Cyclic Nitrones Full article

Journal

Journal of Organic Chemistry
ISSN: 0022-3263

Output data

Year: 2012, Volume: 77, Number: 23, Pages: 10688-10698 Pages count : DOI: 10.1021/jo3019158

Authors

Morozov Denis A. ^1,2 , Kirilyuk Igor A. ¹ , Komarov Denis A. ¹ , Goti Andrea ³ , Bagryanskaya Irina Yu. ¹ , Kuratieva Natalia V. ⁴ , Grigor'ev Igor A. ¹

Affiliations

1	(Данные Web of science) Novosibirsk Organ Chem Inst, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) Univ Florence, Dipartimento Chim Ugo Schiff, I-50019 Florence, Italy
4	(Данные Web of science) Nikolaev Inst Inorgan Chem, Novosibirsk 630090, Russia

A sterically hindered bis-spirocyclic C-2-symmetric chiral pyrrolidine-type nitroxide has been successfully synthesized starting from an L-tartaric derived nitrone. Starting from a pyrrolidine flanked by two methylene groups, complete quaternization of the two alpha-carbon atoms has been accomplished through iteration of completely regio- and stereoselective intramolecular cycloaddition reactions and organometallic additions to key nitrone intermediates, formed in turn by oxidation procedures. This method appears to be very useful for building up bulky spirocyclic moieties adjacent to a nitroxide group and provides an important supplementation to traditional methods of nitroxide synthesis. The synthesized chiral nitroxide showed a very high stability to reduction with ascorbate (k approximate to 8 x 10(-3) M-1 s(-1)).

Morozov D.A. , Kirilyuk I.A. , Komarov D.A. , Goti A. , Bagryanskaya I.Y. , Kuratieva N.V. , Grigor'ev I.A.
Synthesis of a Chiral C-2-Symmetric Sterically Hindered Pyrrolidine Nitroxide Radical via Combined Iterative Nucleophilic Additions and Intramolecular 1,3-Dipolar Cycloadditions to Cyclic Nitrones
Journal of Organic Chemistry. 2012. V.77. N23. P.10688-10698. DOI: 10.1021/jo3019158 WOS Scopus РИНЦ

Published online:	Nov 20, 2012
Published print:	Dec 7, 2012

Web of science	WOS:000311926100023
Scopus	2-s2.0-84870943523
Elibrary	20487251
OpenAlex	W2328856290