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)

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.

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22

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.