4-Dimethylamino-pyridine(DMAP)
2003; Thieme Medical Publishers (Germany); Issue: 10 Linguagem: Inglês
10.1055/s-2003-40867
ISSN1437-2096
Autores Tópico(s)Metabolism and Genetic Disorders
ResumoIn 1969 Steglich and Höfle reported 4-(dimethylamino)-pyridine (DMAP) (1) as a very effective acylation catalyst. [1] Independently, the Russian group of Litvinenko and Kirichenko discovered that pyridine replaced by DMAP accelerates the reaction rate by ca. 10 [4] for the benzoylation of m-chloroaniline. [2] As a result of many investigations based on the fundamental work by Steglich et al., DMAP has been used in a large range of applications as a catalyst for acylation of alcohols, amines, phenols and enolates, [3-5] in particular for the acylation of sterically hindered secondary or tertiary alcohols. For example, 1-methyl-1-cyclohexanol is not acylated under basic conditions (pyridine, Ac2O), whereas in the presence of 4.1 mol% of DMAP a yield of 86% is achieved after 14 hours at room temperature. [1] It should be mentioned that DMAP shows good catalytic activity under certain conditions. Non-polar solvents like pyridine and Ac2O (rather than acid chlorides) are suitable.
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