TEMPO-mediated electro-oxidation reactions of non-phenolic β-O-4-type lignin model compounds

Yumi Sannami; Hiroshi Kamitakahara; Toshiyuki Takano

doi:10.1515/hf-2016-0117

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TEMPO-mediated electro-oxidation reactions of non-phenolic β-O-4-type lignin model compounds

Yumi Sannami , Hiroshi Kamitakahara and Toshiyuki Takano

Published/Copyright: October 29, 2016

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From the journal Holzforschung Volume 71 Issue 2

Abstract

Oxidation reactions of a non-phenolic β-O-4-type lignin model compound [4-ethoxy-3-methoxyphenylglycerol-β-guaiacyl ether (1)] were conducted in an electrolytic mediator system (EMS) using 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO) or 4-acetoamido-TEMPO (AcNH-TEMPO) as mediators. The results revealed that the electrolytes strongly influenced the chemoselectivity between Cα-carbonylation and Cγ-carboxylation of compound 1. The Cα-carbonylation proceeded preferentially in the EMS oxidation conducted in the LiClO₄/CH₃CN-H₂O system, although the yield of the resulting Cα-carbonyl compound 2 was low (1.9%–11.1%). In contrast, Cγ-carbonylation was preferred, if the EMS oxidation reactions were conducted in the dioxane-carbonate buffer (pH 10.0), dioxane-borate buffer (pH 10.0), and dioxane-phosphate buffer (pH 7.0). Especially, the Cγ-carboxyl compound 3 was obtained in a high yield (72.0%–93.2%), when the dioxane-phosphate buffer served as the electrolyte. The catalytic efficiency of AcNH-TEMPO was higher than that of TEMPO for the EMS oxidation reactions. The conclusion is that AcNH-TEMPO-EMS oxidation reaction in dioxane-phosphate buffer could be used for the chemoselective Cγ-carboxylation of lignins.

Keywords: 4-acetoamido-TEMPO (AcNH-TEMPO); Cα-carbonylation; Cγ-carboxylation; electrolytic mediator system (EMS); lignin; 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO)

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Received: 2016-7-25

Accepted: 2016-9-28

Published Online: 2016-10-29

Published in Print: 2017-2-1

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Articles in the same Issue

https://doi.org/10.1515/hf-2016-0117

Keywords for this article

4-acetoamido-TEMPO (AcNH-TEMPO); Cα-carbonylation; Cγ-carboxylation; electrolytic mediator system (EMS); lignin; 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO)