Capricious Selectivity in Electrophilic Deuteration of Methylenedioxy Substituted Aromatic Compounds

Capricious Selectivity in Electrophilic Deuteration of Methylenedioxy Substituted Aromatic Compounds

Ring deuteration via the SEAr mechanism, which is usually problem-free, is found to be troublesome with methylenedioxy substituent aromatics. We report a case where the deuteration not only partially fails at one of the ortho positions but also is completely prevented by a conformation dependent eff...

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Bibliographic Details
Published in:Journal of organic chemistry Vol. 79; no. 21; pp. 10636 - 10640
Main Authors: Pohjoispää, Monika, Mera-Adasme, Raúl, Sundholm, Dage, Heikkinen, Sami, Hase, Tapio, Wähälä, Kristiina
Format: Journal Article
Language:English
Published: United States American Chemical Society 07-11-2014
Subjects:
Benzene Derivatives - chemistry
Dioxoles - chemistry
Magnetic Resonance Spectroscopy
Models, Molecular
Organic Chemicals
Quantum Theory
Online Access:Get full text
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Summary:Ring deuteration via the SEAr mechanism, which is usually problem-free, is found to be troublesome with methylenedioxy substituent aromatics. We report a case where the deuteration not only partially fails at one of the ortho positions but also is completely prevented by a conformation dependent effect at the other o-position. Such selectivity discrepancies are important due to the widespread occurrence of methylenedioxy substituted natural products. Density functional theory calculations were used to elucidate the exchange reaction mechanism in 1,2-dialkoxybenzenes.
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ISSN:0022-3263
1520-6904
DOI:10.1021/jo5019427