Synthesis 2017; 49(15): 3460-3470
DOI: 10.1055/s-0036-1588854
paper
© Georg Thieme Verlag Stuttgart · New York

Chemoselectivity in Esterification Reactions – Size Matters after All

Julian Helberg
Department of Chemistry, LMU München, Butenandtstrasse 5–13, 81377 München, Germany   Email: zipse@cup.uni-muenchen.de
,
Marta Marin-Luna
Department of Chemistry, LMU München, Butenandtstrasse 5–13, 81377 München, Germany   Email: zipse@cup.uni-muenchen.de
,
Department of Chemistry, LMU München, Butenandtstrasse 5–13, 81377 München, Germany   Email: zipse@cup.uni-muenchen.de
› Author Affiliations
This work was financially supported by the Deutsche Forschungsgemeinschaft (DFG) through the Priority Program ‘Control of London Dispersion Interactions in Molecular Chemistry’ (SPP 1087). Marta Marin-Luna thanks the ‘Xunta de Galicia’ for her contract (ED481B 2016/166-0).
Further Information

Publication History

Received: 05 May 2017

Accepted: 08 May 2017

Publication Date:
13 June 2017 (eFirst)

Dedicated to Herbert Mayr on the occasion of his 70th birthday

Abstract

The reaction of carboxylic acid chlorides with secondary alcohols carrying either flexible alkyl or rigid aryl substituents was studied through a series of competition experiments. Aliphatic acid chlorides react preferentially with the aryl-substituted alcohols, while acid chlorides derived from aromatic carboxylic acids react with very low selectivity. Catalysis by 9-azajulolidine (TCAP) increases the selectivity strongly, while solvent and temperature effects are only moderate. The size of the alcohol substituents seems to impact selectivities only for rigid aryl substituents, and highest selectivities have been found for 1-(1-pyrenyl)ethanol.

Supporting Information

 
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