Thermoresponsive Polymer-Supported l-Proline Micelle Catalysts for the Direct Asymmetric Aldol Reaction in Water

Hazit A. Zayas, Annhelen Lu, David Valade, Faheem Amir, Zhongfan Jia, Rachel K. O'Reilly, Michael J. Monteiro

Research output: Contribution to journalArticlepeer-review

96 Citations (Scopus)

Abstract

l-Proline moieties bound to a thermoresponsive polymer nanoreactor efficiently directed the asymmetric aldol reaction in water with excellent yields and enantioselectivity (ee). The reactions were efficient at higher temperatures in direct contrast to the low yields and ee values found when the reaction was carried out in a DMF/water mixture due to the location of the l-proline moieties within the hydrophobic pocket inside the core of the nanoreactors. This ideal environment formed for catalysis allows control over the water content as well as enhancing interactions between the carboxylic acid of l-proline and the aldehyde substrate. The nanoreactors were disassembled to fully water-soluble polymers by lowering the temperature to below the lower critical solution temperature (LCST) of the polymer, resulting in precipitation of the product in near pure form. The product was isolated by centrifugation and the polymer/water solution reused in additional catalytic cycles by heating the polymer above its LCST and thus reforming the nanoreactors. Although a small decrease in yield after five cycles was observed, the selectivity (anti/syn ratio and ee) remained high.

Original languageEnglish
Pages (from-to)327-331
Number of pages5
JournalACS Macro Letters
Volume2
Issue number4
DOIs
Publication statusPublished - 16 Apr 2013
Externally publishedYes

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