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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\u2010free access to \u03b1,\u03b2\u2010unsaturated aldehydes from alkenes with formaldehyde. This reaction is catalyzed by dimethylamine and affords \u03b1,\u03b2\u2010unsaturated aldehydes in yields of up to 80\u2009%. 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\u201350\u2009\u00b0C), in a theoretically 100\u2009% carbon\u2010economical fashion, with water as the only by\u2010product. The reaction was successfully applied to non\u2010activated linear 1\u2010alkenes, thus opening an access to industrially relevant \u03b1,\u03b2\u2010unsaturated aldehydes from cheap and widely abundant chemicals at large scale.<\/jats:p>","DOI":"10.1002\/chem.202400601","type":"journal-article","created":{"date-parts":[[2024,3,16]],"date-time":"2024-03-16T02:33:58Z","timestamp":1710556438000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Metal\u2010Free Selective Synthesis of \u03b1,\u03b2\u2010Unsaturated Aldehydes from Alkenes and Formaldehyde Catalyzed by Dimethylamine"],"prefix":"10.1002","volume":"30","author":[{"given":"Gongming","family":"Peng","sequence":"first","affiliation":[{"name":"Eco-Efficient Products and Process Laboratory  Syensqo\/CNRS 3966 Jin Du Rd., Xin Zhuang Industrial Zone Shanghai 201108 China."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Naseeb","family":"Ullah","sequence":"additional","affiliation":[{"name":"Institut de Chimie des Milieux et Mat\u00e9riaux de Poitiers University of Poitiers-CNRS  1 rue Marcel Dor\u00e9, TSA 41105, 86073 Poitiers France."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"St\u00e9phane","family":"Streiff","sequence":"additional","affiliation":[{"name":"Eco-Efficient Products and Process Laboratory  Syensqo\/CNRS 3966 Jin Du Rd., Xin Zhuang Industrial Zone Shanghai 201108 China."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Karine","family":"De Oliveira Vigier","sequence":"additional","affiliation":[{"name":"Institut de Chimie des Milieux et Mat\u00e9riaux de Poitiers University of Poitiers-CNRS  1 rue Marcel Dor\u00e9, TSA 41105, 86073 Poitiers France."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marc","family":"Pera\u2010Titus","sequence":"additional","affiliation":[{"name":"Eco-Efficient Products and Process Laboratory  Syensqo\/CNRS 3966 Jin Du Rd., Xin Zhuang Industrial Zone Shanghai 201108 China."},{"name":"Cardiff Catalysis Institute School of Chemistry Cardiff University  Main Building, Park Place Cardiff CF10 3AT UK"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Raphael","family":"Wischert","sequence":"additional","affiliation":[{"name":"Eco-Efficient Products and Process Laboratory  Syensqo\/CNRS 3966 Jin Du Rd., Xin Zhuang Industrial Zone Shanghai 201108 China."},{"name":"Syensqo R&amp;I Center Lyon  85 Av. des Fr\u00e8res Perret 69190 Saint-Fons France."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8324-0119","authenticated-orcid":false,"given":"Fran\u00e7ois","family":"J\u00e9r\u00f4me","sequence":"additional","affiliation":[{"name":"Institut de Chimie des Milieux et Mat\u00e9riaux de Poitiers University of Poitiers-CNRS  1 rue Marcel Dor\u00e9, TSA 41105, 86073 Poitiers France."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,4,8]]},"reference":[{"key":"e_1_2_7_1_1","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.2174\/1570193X16666190617155058"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/ajoc.201900275"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.3390\/molecules26144297"},{"key":"e_1_2_7_5_1","unstructured":"\u00a0"},{"key":"e_1_2_7_6_2","doi-asserted-by":"crossref","unstructured":"D. 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