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However, direct access to C-glycosides with control of stereochemistry from readily available, bench-stable, and cost-effective starting materials remains a formidable challenge. Herein, a Ni-catalyzed chemo- and regioselective iterative hydrocarbonylation of glycals with alkenes for the synthesis of stereodivergent C-acylated glycosides has been developed, representing the first example of synthesizing C-acylated glycosides from glycals. The reaction tolerates a wide range of glycals and unactivated alkenes, affording corresponding C-glycosides with diverse substitution patterns. Moreover, cross-carbonylation of primary\u2013secondary and more sterically hindered secondary\u2013secondary alkyl metallic intermediates was achieved, providing access to 2-deoxygenated C-glycosides from glycals without using any glycosyl electrophiles or alkyl electrophiles. Notably, both \u03b1- and \u03b2-anomers could be easily obtained with high diastereoselectivity, rendering this protocol useful for the synthesis of C-glycosides using alkenes as the sole coupling precursors.<\/jats:p>","DOI":"10.1021\/jacs.6c13660","type":"journal-article","created":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T10:02:15Z","timestamp":1791453735000},"page":"44639-44648","source":"Crossref","is-referenced-by-count":0,"title":["Stereodivergent Synthesis\nof\n                    <i>C<\/i>\n                    -Glycosides\nfrom Glycals by Ni-Catalyzed Cross-Hydrocarbonylation of Alkenes"],"prefix":"10.1021","volume":"148","author":[{"given":"Cheng-Tao","family":"Wang","sequence":"first","affiliation":[{"name":"Xinjiang University , , ,","place":["Urumqi, Xinjiang, P. R. China, 830017"]},{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, Guangdong, P. R. China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yun-Long","family":"Xia","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, Guangdong, P. R. China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xing-Fu","family":"Wei","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, Guangdong, P. R. China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jia-Ni","family":"Lin","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, Guangdong, P. R. China, 518055"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiong","family":"Yu","sequence":"additional","affiliation":[{"name":"Southern University of Science and Technology , , ,","place":["Shenzhen, Guangdong, P. R. 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A Synthesis of \u03b1-D-C-Glycosides","volume":"26","author":"Beau","year":"1985","journal-title":"Tetrahedron Lett."},{"key":"2026102111072299800_cit44","doi-asserted-by":"publisher","first-page":"131955","DOI":"10.1016\/j.tet.2021.131955","article-title":"A General\nApproach to C-Acyl Glycosides via Palladium\/Copper\nCo-Catalyzed Coupling Reaction of Glycosyl Carbothioates and Arylboronic\nAcids","volume":"82","author":"Wang","year":"2021","journal-title":"Tetrahedron"},{"key":"2026102111072299800_cit45","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202202619","article-title":"Efficient\nCopper-Catalyzed Highly Stereoselective Synthesis of Unprotected C-Acyl Manno-Rhamno- and Lyxopyranosides","volume":"28","author":"Boehlich","year":"2022","journal-title":"Chem. Eur. 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