Lewis Acid Triggered Vinylcyclopropane-Cyclopentene Rearrangement

We report a mild Lewis acid induced isomerization of donor-acceptor cyclopropanes, containing an alkenyl moiety and diverse electron-withdrawing group(s) at the adjacent positions, into substituted cyclopentenes. We have found that 1,1,2-trisubstituted cyclopent-3-enes were exclusively obtained in yield of 51-99% when cyclopropanes with a 2-substituted alkenyl group as a donor underwent isomerization. For cyclopropanes bearing a trisubstituted alkenyl group either the corresponding cyclopent-3-enes or isomeric cyclopent-2-enes having two acceptor groups at the C(1) atom were formed, with the reaction selectivity being determined by the applied Lewis acid. We have shown that the reactivity of the donor-acceptor cyclopropane increases with the increase of the electron-donating character of (hetero)aromatic group attached to the alkenyl moiety. The synthetic utility of the developed methodology was also demonstrated through the synthesis of polysubstituted cyclopentane and piperidine derivatives. © 2017 American Chemical Society.

Авторы
Ivanova O.A. 1 , Chagarovskiy A.O. 2, 3 , Shumsky A.N.4 , Krasnobrov V.D.1 , Levina I.I.4 , Trushkov I.V. 2, 3
Журнал
Journal of Organic Chemistry
Номер выпуска
2
Язык
Английский
Страницы
543-560
Статус
Опубликовано
Ссылка
Внешняя ссылка
DOI
10.1021/ACS.JOC.7B02351
Том
83
Год
2018
Организации
  • 1 Department of Chemistry, M.V. Lomonosov Moscow State University, Leninskie Gory 1-3, Moscow, 119991, Russian Federation
  • 2 Dmitry Rogachev National Research Center of Pediatric Hematology, Oncology and Immunology, Samory Mashela 1, Moscow, 117997, Russian Federation
  • 3 Faculty of Science, RUDN University, Miklukho-Maklaya 6, Moscow, 117198, Russian Federation
  • 4 Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina 4, Moscow, 119334, Russian Federation
Ключевые слова
Isomerization; Isomers; Acceptor groups; Aromatic group; Donor-acceptor cyclopropanes; Electron withdrawing group; Electron-donating; Reaction selectivity; Synthetic utility; Vinylcyclopropane; Propane; 2 (2 phenylethenyl)spiro(cyclopropane 1,2' indene] 1',3' dione; 2 [2 (4 methoxyphenyl)ethenyl] 1' methylspiro[cyclopropane 1,3' indolin] 2' one; alkenyl group; cyclopent 2 ene derivative; cyclopent 3 ene derivative; cyclopentane derivative; cyclopentene derivative; cyclopropane derivative; dimethyl 2 (2 methoxyphenyl)cyclopent 3 ene 1,1 dicarboxylate; dimethyl 2 (3 chlorophenyl)cyclopent 3 ene 1,1 dicarboxylate; dimethyl 2 (4 chlorophenyl)cyclopent 3 ene 1,1 dicarboxylate; dimethyl 2 (4 methoxyphenyl)cyclopent 3 ene 1,1 dicarboxylate; dimethyl 2 phenylcyclopent 3 ene 1,1 dicarboxylate; dimethyl 2 [1 (4 fluoropheny)lprop 1 en 2 yl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [1 phenylprop 1 en 2 yl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 (2 methoxyphenyl)ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 (2 nitrophenyl)ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 (3 chlorophenyl)ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 (4 chlorophenyl)ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 (furan 2 yl)ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 (thiophene 2 yl)ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [2 [4 (dimethylphenyl)phenyl]ethenyl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [3 phenyl 1 (thiophene 2 yl)lprop 1 en 2 yl]cyclopropane 1,1 dicarboxylate; dimethyl 2 [4 (dimethylamino)phenyl]cyclopent 3 ene 1,1 dicarboxylate; Lewis acid; methyl 1 (dimethoxyphosphoryl) 2 [2 (4 methoxyphenyl)ethenyl]cyclopropanecarboxylate; methyl 1 cyano 2 (2 phenylethenyl)cyclopropane 1 carboxylate; methyl 1 cyano 2 [2 (4 methoxyphenyl)ethenyl]cyclopropane 1 carboxylate; piperidine derivative; unclassified drug; vinylcyclopropane; Article; chemical structure; isomerization; substitution reaction
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