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Issue 20, 2013
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Lanthanum(iii) catalysts for highly efficient and chemoselective transesterification

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Abstract

A facile, atom-economical, and chemoselective esterification is crucial in modern organic synthesis, particularly in the areas of pharmaceutical, polymer, and material science. However, a truly practical catalytic transesterification of carboxylic esters with various alcohols has not yet been well established, since, with many conventional catalysts, the substrates are limited to 1°- and cyclic 2°-alcohols. In sharp contrast, if we take advantage of the high catalytic activities of La(Oi-Pr)3, La(OTf)3, and La(NO3)3 as ligand-free catalysts, ligand-assisted or additive-enhanced lanthanum(III) catalysts can be highly effective acid–base combined catalysts in transesterification. A highly active dinuclear La(III) catalyst, which is prepared in situ from lanthanum(III) isopropoxide and 2-(2-methoxyethoxy)ethanol, is effective for the practical transesterification of methyl carboxylates, ethyl acetate, weakly reactive dimethyl carbonate, and much less-reactive methyl carbamates with 1°-, 2°-, and 3°-alcohols. As the second generation, nearly neutral “lanthanum(III) nitrate alkoxide”, namely La(OR)m(NO3)3−m, has been developed. This catalyst is prepared in situ from inexpensive, stable, low-toxic lanthanum(III) nitrate hydrate and methyltrioctylphosphonium methyl carbonate, and is highly useful in the non-epimerized transesterification of α-substituted chiral carboxylic esters, even under azeotropic reflux conditions. In these practical La(III)-catalyzed transesterifications, colorless esters can be obtained in small- to large-scale synthesis without the need for inconvenient work-up or careful purification procedures.

Graphical abstract: Lanthanum(iii) catalysts for highly efficient and chemoselective transesterification

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Article information


Submitted
14 Nov 2012
Accepted
14 Dec 2012
First published
17 Jan 2013

Chem. Commun., 2013,49, 1983-1997
Article type
Feature Article

Lanthanum(III) catalysts for highly efficient and chemoselective transesterification

M. Hatano and K. Ishihara, Chem. Commun., 2013, 49, 1983
DOI: 10.1039/C2CC38204K

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