{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Prusinowski AF"],"funding":["Division of Chemistry","NCRR NIH HHS","National Institute of General Medical Sciences","NIGMS NIH HHS"],"pagination":["5429-5438"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC7299201"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["142(11)"],"pubmed_abstract":["A double functionalization of <i>vicinal sp</i><sup>3</sup> C-H bonds has been developed, wherein a β amine and γ iodide are incorporated onto an aliphatic alcohol in a single operation. This approach is enabled by an imidate radical chaperone, which selectively affords a transient β alkene that is amino-iodinated in situ. Overall, the radical-polar-crossover cascade entails the following key steps: (i) β C-H iodination via 1,5-hydrogen atom transfer (HAT), (ii) desaturation via I<sub>2</sub> complexation, and (iii) <i>vicinal</i> amino-iodination of an in situ generated allyl imidate. The synthetic utility of this double C-H functionalization is illustrated by conversion of aliphatic alcohols to a diverse collection of α,β,γ substituted products bearing heteroatoms on three adjacent carbons. The radical-polar crossover mechanism is supported by various experimental probes, including isotopic labeling, intermediate validation, and kinetic studies."],"journal":["Journal of the American Chemical Society"],"pubmed_title":["<i>Vicinal</i>, Double C-H Functionalization of Alcohols via an Imidate Radical-Polar Crossover Cascade."],"pmcid":["PMC7299201"],"funding_grant_id":["S10 RR027172","CAREER 1654656","R35 GM119812"],"pubmed_authors":["Prusinowski AF","Wappes EA","Twumasi RK","Nagib DA"],"additional_accession":[]},"is_claimable":false,"name":"<i>Vicinal</i>, Double C-H Functionalization of Alcohols via an Imidate Radical-Polar Crossover Cascade.","description":"A double functionalization of <i>vicinal sp</i><sup>3</sup> C-H bonds has been developed, wherein a β amine and γ iodide are incorporated onto an aliphatic alcohol in a single operation. This approach is enabled by an imidate radical chaperone, which selectively affords a transient β alkene that is amino-iodinated in situ. Overall, the radical-polar-crossover cascade entails the following key steps: (i) β C-H iodination via 1,5-hydrogen atom transfer (HAT), (ii) desaturation via I<sub>2</sub> complexation, and (iii) <i>vicinal</i> amino-iodination of an in situ generated allyl imidate. The synthetic utility of this double C-H functionalization is illustrated by conversion of aliphatic alcohols to a diverse collection of α,β,γ substituted products bearing heteroatoms on three adjacent carbons. The radical-polar crossover mechanism is supported by various experimental probes, including isotopic labeling, intermediate validation, and kinetic studies.","dates":{"release":"2020-01-01T00:00:00Z","publication":"2020 Mar","modification":"2025-04-04T01:45:56.157Z","creation":"2025-04-04T01:45:56.157Z"},"accession":"S-EPMC7299201","cross_references":{"pubmed":["32141741"],"doi":["10.1021/jacs.0c01318"]}}