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Demonstrated here is that formic acid mediates the Rh\u2010catalyzed,<jats:italic>Z<\/jats:italic>\u2010selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active Rh intermediate by ligand dissociation is the rate\u2010determining step. The rapid generation and trapping of Rh\u2010allyl intermediates is key to preventing chain\u2010walking isomerization events that plague related protocols. Insights gained through this study may have wider implications in selective metal\u2010catalyzed hydrofunctionalization reactions.<\/jats:p>","DOI":"10.1002\/anie.201905540","type":"journal-article","created":{"date-parts":[[2019,6,19]],"date-time":"2019-06-19T01:44:05Z","timestamp":1560908645000},"page":"12246-12251","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["Direct Formic Acid Mediated<i>Z<\/i>\u2010Selective Reductive Coupling of Dienes and Aldehydes"],"prefix":"10.1002","volume":"58","author":[{"given":"Christopher","family":"Cooze","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Alberta Edmonton Alberta T6G 2G2 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Raphael","family":"Dada","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Alberta Edmonton Alberta T6G 2G2 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7760-6946","authenticated-orcid":false,"given":"Rylan J.","family":"Lundgren","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Alberta Edmonton Alberta T6G 2G2 Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2019,7,24]]},"reference":[{"key":"e_1_2_7_1_1","volume-title":"Handbook of Functionalized Organometallics: Applications in Synthesis","year":"2005"},{"key":"e_1_2_7_2_1","unstructured":"\u00a0"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300634"},{"key":"e_1_2_7_3_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200300634"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1351\/pac200880050929"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2013.08.109"},{"key":"e_1_2_7_6_1","unstructured":"\u00a0"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aah5133"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00213"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200802938"},{"key":"e_1_2_7_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200802938"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.7b00308"},{"key":"e_1_2_7_11_1","unstructured":"For selected examples see:"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aaf7720"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja5130258"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201704248"},{"key":"e_1_2_7_14_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201704248"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201609056"},{"key":"e_1_2_7_15_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201609056"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b13309"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b13907"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b13652"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3sc22051f"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b01784"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201900801"},{"key":"e_1_2_7_21_3","doi-asserted-by":"crossref","first-page":"2007","DOI":"10.1002\/ange.201813117","volume":"131","year":"2019","journal-title":"Angew. 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