Working Paper
Authors
- Demelza Lyons ,
- Claire Empel ,
- Domenic Pace ,
- An Huy Dinh ,
- Binh Khanh Mai ,
- Rene Koenigs ,
- Thanh Vinh Nguyen
University of New South Wales, Sydney
Abstract
Acyl transfer catalysis is a frequently used tool to promote the formation of carboxylic acid derivatives, which are important synthetic precursors and target compounds in organic synthesis. However, there have been only a few structural motifs known to efficiently catalyze the acyl transfer reaction. Herein we introduce a new acyl transfer catalytic paradigm based on the tropolone framework. We show that tropolonate salts, due to their strong nucleophilicity and photochemical activity, can promote the coupling reaction between alcohols and carboxylic acid anhydrides or chlorides to give the products with excellent efficiency under thermal or blue light-photochemical conditions. Kinetic studies and density functional theory (DFT) calculations suggest interesting mechanistic insights for reactions promoted by this new acyl transfer catalytic system.
Content
![Thumbnail image of Tropolonate[10]_ChemRxiv.pdf](https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/60c74ef80f50db4f18397300/largeThumb/tropolonate-salts-as-acyl-transfer-catalysts-for-esterification-reactions-under-thermal-and-photochemical-conditions.jpg)
Supplementary material

TOC
![Thumbnail image of Tropolonate_SI1_Experimental[8].pdf](https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/60c74ef9469df4c5cef445be/largeThumb/tropolonate-si1-experimental-8.jpg)
Tropolonate SI1 Experimental[8]
![Thumbnail image of Tropolonate_SI2_Computational[9].pdf](https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/60c74ef9702a9ba9a818bab3/largeThumb/tropolonate-si2-computational-9.jpg)
Tropolonate SI2 Computational[9]