Resolution and rotational barriers of quinolinone and acridone sulfenamide derivatives: Demonstration of the S-N chiral axis

M. B.D. Blanca, C. Yamamoto, Y. Okamoto, S. E. Biali*, D. Kost

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

Achiral (8a) and chiral (8b) N-(2,4-dinitrobenzenesulfenyl)acridone derivatives were synthesized. Addition of the chiral solvating agent (S)- 2,2,2-trifluro-1-(anthryl)ethanol to 8a rendered the enantiotopic groups on the acridone ring diastereotopic and anisochronous, thus allowing the estimation of a lower limit for the rotational barrier about the S-N bond (18.7 kcal mol-1) by NMR spectroscopy. 8b and the previously reported chiral sulfenamide 5 (Raban, M.; Martin, V. A.; Craine, L. J. Org. Chem. 1990, 55, 4311) were resolved on a Chiracel OD HPLC column. This constitutes the first resolution of stereostable enantiomers of a compound in which the chirality is due only to the presence of the S-N chiral axis. The rotational barriers of both compounds are nearly equal (22.7-22.8 kcal mol-1 at 303.7 K) and are the largest determined to date for the rotation about the S-N bond in sulfenamides. The relatively high enantiomerization barrier for 8b is remarkable since the peri positions are unsubstituted.

Original languageAmerican English
Pages (from-to)8613-8620
Number of pages8
JournalJournal of Organic Chemistry
Volume65
Issue number25
DOIs
StatePublished - 15 Dec 2000

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