Metal‐free selective synthesis of α,β‐unsaturated aldehydes from alkenes and formaldehyde catalyzed by dimethylamine

Peng, Gongming, Ullah, Naseeb, Streiff, Stéphane, De Oliveira Vigier, Karine, Pera‐Titus, Marc, Wischert, Raphael and Jérôme, François 2024. Metal‐free selective synthesis of α,β‐unsaturated aldehydes from alkenes and formaldehyde catalyzed by dimethylamine. Chemistry - A European Journal 30 (29) , e202400601. 10.1002/chem.202400601

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Abstract

α,β‐Unsaturated aldehydes are important building blocks for the synthesis of a wide range of chemicals, including polymers. The synthesis of these molecules from cheap feedstocks such as alkenes remains a scientific challenge, mainly due to the low reactivity of alkenes. Here we report a selective and metal‐free access to α,β‐unsaturated aldehydes from alkenes with formaldehyde. This reaction is catalyzed by dimethylamine and affords α,β‐unsaturated aldehydes in yields of up to 80 %. By combining Density Functional Theory (DFT) calculations and experiments, we elucidate the reaction mechanism which is based on a cascade of hydride transfer, hydrolysis and aldolization reactions. The reaction can be performed under very mild conditions (30–50 °C), in a theoretically 100 % carbon‐economical fashion, with water as the only by‐product. The reaction was successfully applied to non‐activated linear 1‐alkenes, thus opening an access to industrially relevant α,β‐unsaturated aldehydes from cheap and widely abundant chemicals at large scale.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Additional Information:	License information from Publisher: LICENSE 1: URL: http://creativecommons.org/licenses/by/4.0/
Publisher:	Wiley
ISSN:	0947-6539
Date of First Compliant Deposit:	9 April 2024
Date of Acceptance:	14 March 2024
Last Modified:	10 Jun 2024 11:28
URI:	https://orca.cardiff.ac.uk/id/eprint/167837

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