Iridium‐Catalyzed Linear‐Selective sp ³ C−H Alkylation of <i>N</i> ‐Methylamides Using Alkenes Enabled by Diphosphite Ligands

An iridium-catalyzed linear-selective sp³ C─H alkylation of N-methylamides with alkenes was developed using bulky, electron-deficient diphosphite ligands. The reaction accommodates N-methylacetamide derivatives bearing diverse substituents and a range of terminal alkenes. Mechanistic studies were conducted to gain insights into the reaction pathway. Internal alkenes can also be used via in situ consecutive alkene isomerization. Selective sp³ C─H functionalization was achieved even in the presence of competing sp² C─H bonds.