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Meanwhile their use in alkylation processes has been somehow limited due to their inherent difficulty in evolving to less\u2010stable radicals after sulfur dioxide extrusion. Herein we report a convenient strategy that involves<jats:italic>gem<\/jats:italic>\u2010difluorinated sulfinates as an \u201cupgrading\u2010mask\u201d, allowing these precursors to decompose into their corresponding alkyl radicals. The electron\u2013donor character of sulfinates in the formation of an electron donor\u2013acceptor (EDA) complex with transient iminium ions is displayed, achieving the first example of a stereocontrolled light\u2010driven insertion of<jats:italic>gem<\/jats:italic>\u2010difluoro derivatives into unsaturated aldehydes. This methodology is compatible with flow conditions, maintaining identical levels of enantiocontrol.<\/jats:p>","DOI":"10.1002\/anie.202112632","type":"journal-article","created":{"date-parts":[[2022,1,4]],"date-time":"2022-01-04T15:49:31Z","timestamp":1641311371000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":57,"title":["Fluorinated Sulfinates as Source of Alkyl Radicals in the Photo\u2010Enantiocontrolled \u03b2\u2010Functionalization of Enals"],"prefix":"10.1002","volume":"61","author":[{"given":"Ricardo I.","family":"Rodr\u00edguez","sequence":"first","affiliation":[{"name":"Organic Chemistry Department M\u00f3dulo 1 Universidad Aut\u00f3noma de Madrid 28049 Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9382-2622","authenticated-orcid":false,"given":"Marina","family":"Sicignano","sequence":"additional","affiliation":[{"name":"Organic Chemistry Department M\u00f3dulo 1 Universidad Aut\u00f3noma de Madrid 28049 Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9154-4067","authenticated-orcid":false,"given":"Jos\u00e9","family":"Alem\u00e1n","sequence":"additional","affiliation":[{"name":"Organic Chemistry Department M\u00f3dulo 1 Universidad Aut\u00f3noma de Madrid 28049 Madrid Spain"},{"name":"Institute for Advanced Research in Chemical Sciences (IAdChem) Universidad Aut\u00f3noma de Madrid 28049 Madrid Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,1,19]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","unstructured":"J.\u2005I. 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