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Synthesis 2007(8): 1185-1196  
DOI: 10.1055/s-2007-965973
PAPER
© Georg Thieme Verlag Stuttgart · New York

Modular Design of Pyridine-Based Acyl-Transfer Catalysts

Ingmar Held, Shangjie Xu, Hendrik Zipse*
Department Chemie und Biochemie, LMU München, Butenandtstraße 5-13, 81377 München, Germany
Fax: +49(89)218077738; e-Mail: zipse@cup.uni-muenchen.de;
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Publikationsverlauf

Received 24 January 2007
Publikationsdatum:
28. Februar 2007 (online)

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Abstract

Derivatives of 3,4-diaminopyridine have been synthesized and studied as catalysts for acyl-transfer reactions. The design of these catalysts is guided by the stability of their acetyl intermediates as determined through theoretical calculations at the B3LYP/6-311 + G(d,p)//B3LYP/6-31G(d) level of theory. The most promising catalysts have been synthesized through a three- to five-step synthesis starting from 3,4-diaminopyridine. The catalytic activity has been determined for the acylation of 1-ethynylcyclohexanol with acetic anhydride at 23 °C and with isobutyric anhydride at 40 °C. For both reactions, the catalytic activity depends dramatically on the substitution pattern of the diaminopyridines. Best results are obtained with catalysts containing alkyl substituents at both amine nitrogens.

Key words

catalysis - nucleophilic pyridines - acylation - alcohols

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The rate of reaction in these cases is hardly different from that of the uncatalyzed background reaction, making the exact determination of the half-lives rather difficult with the methodology employed here. The data given in Table [2] have been estimated from the conversion measured for reaction A up to 25 d, 17 h and 30 min and for reaction B up to 31 d, 17 h and 15 min. In both cases the reactions had not yet reached 50% conversion at these times.

23

The conversion of the reaction stopped at 59%. ESI-MS studies of the reaction mixture indicate that the catalyst does not survive the reaction conditions employed here.