{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Turro RF"],"funding":["Division of Chemistry","State Key Laboratory of Green Chemistry-Synthesis Technology, Zhejiang University of Technology","Fundamental Research Funds for the Provincial Universities of Zhejiang","National Natural Science Foundation of China","National Institute of General Medical Sciences","NIGMS NIH HHS","Division of Graduate Education"],"pagination":["14705-14715"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC10347553"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["145(27)"],"pubmed_abstract":["Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of <i>N</i>-hydroxyphthalimide (NHP) esters and benzylic chlorides are reported. Investigations of the redox properties of the Ni-bis(oxazoline) catalyst, the reaction kinetics, and mode of electrophile activation show divergent mechanisms for these two related transformations. Notably, the mechanism of C(sp<sup>3</sup>) activation changes from a Ni-mediated process when benzyl chlorides and Mn<sup>0</sup> are used to a reductant-mediated process that is gated by a Lewis acid when NHP esters and tetrakis(dimethylamino)ethylene is used. Kinetic experiments show that changing the identity of the Lewis acid can be used to tune the rate of NHP ester reduction. Spectroscopic studies support a Ni<sup>II</sup>-alkeny"],"journal":["Journal of the American Chemical Society"],"pubmed_title":["Mechanistic Investigation of Ni-Catalyzed Reductive Cross-Coupling of Alkenyl and Benzyl Electrophiles."],"pmcid":["PMC10347553"],"funding_grant_id":["R35GM118191","21978272","DGE-1144469","R35 GM118191","R35-GM142595","R35 GM142595","RF-C2022006","CHE-1764328"],"pubmed_authors":["Wahlman JLH","Hadt RG","Yang YF","Reisman SE","Hong X","Chen EP","Yang M","Houk KN","Turro RF","Chen X","Tong ZJ"],"additional_accession":[]},"is_claimable":false,"name":"Mechanistic Investigation of Ni-Catalyzed Reductive Cross-Coupling of Alkenyl and Benzyl Electrophiles.","description":"Mechanistic investigations of the Ni-catalyzed asymmetric reductive alkenylation of <i>N</i>-hydroxyphthalimide (NHP) esters and benzylic chlorides are reported. Investigations of the redox properties of the Ni-bis(oxazoline) catalyst, the reaction kinetics, and mode of electrophile activation show divergent mechanisms for these two related transformations. Notably, the mechanism of C(sp<sup>3</sup>) activation changes from a Ni-mediated process when benzyl chlorides and Mn<sup>0</sup> are used to a reductant-mediated process that is gated by a Lewis acid when NHP esters and tetrakis(dimethylamino)ethylene is used. Kinetic experiments show that changing the identity of the Lewis acid can be used to tune the rate of NHP ester reduction. Spectroscopic studies support a Ni<sup>II</sup>-alkeny","dates":{"release":"2023-01-01T00:00:00Z","publication":"2023 Jul","modification":"2026-06-04T04:19:11.631Z","creation":"2026-05-04T03:14:10.972Z"},"accession":"S-EPMC10347553","cross_references":{"pubmed":["37358565"],"doi":["10.1021/jacs.3c02649"]}}