Spectrometry and Reactivity of the 1-Hydropyrenyl Anion

Mark A. Hempenius, Cees Erkelens, Patrick P.J. Mulder, Han Zuilhof, Wouter Heinen, Johan Lugtenburg, Jan Cornelisse*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

10 Citations (Scopus)

Abstract

A study of the charge distribution in the 1-hydropyrenyl anion (2), and of its regioselectivity toward electrophilic attack was undertaken. In order to obtain reliable information on the reactive positions in 2, a model with the same conjugated system was prepared, which has its 1-position fixed with a spirocyclopentane ring. Highly resolved 1H and 13C NMR spectra of this spirotcyclopentane-1,1′-[1H]pyrenyl] anion (1) and of 2 were obtained. These spectra could be completely assigned by means of COSY, NOESY, and 2D 1H-13C COSY techniques. According to the 13C NMR measurements, 5-C of 1 and 2 bears the highest negative charge. The results of PM3 semiempirical calculations support this finding and, furthermore, a large HOMO coefficient was calculated at the quaternary 3a-C of 2, suggesting that this position is susceptible toward attack by soft electrophiles. In full agreement with the 13C NMR and PM3 results, 5-C of 1 and 2 show the highest reactivity toward electrophilic attack, while the quaternary 3a-C of 1 and 2 is attacked by soft electrophiles. These new results contradict earlier findings because until now, carbon atom 9-C of the 1-hydropyrenyl anion (2) was assumed to be the most reactive position, and soft electrophiles were thought to attack 10a-C of 2.

Original languageEnglish
Pages (from-to)3076-3084
Number of pages9
JournalJournal of organic chemistry
Volume58
Issue number11
DOIs
Publication statusPublished - 1993
Externally publishedYes

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