Unprecedented enantioselective intramolecular Heck carbonylation reactions of arenediazonium salts were enabled by a chiral N,N ligand. This reaction constitutes the first enantioselective Heck carbonylation that proceeds through migratory insertion followed by CO insertion. The enantioenriched functionalized dihydrobenzofurans were obtained in good to high yields and enantiomeric ratios of up to 98:2 under mild and operationally simple reaction conditions.

Unprecedented enantioselective intramolecular Heck carbonylation reactions of arenediazonium salts were enabled by ac hiral N,Nligand. This reaction constitutes the first enantioselective Heckc arbonylation that proceeds through migratory insertion followed by CO insertion. The enantioenriched functionalizedd ihydrobenzofurans were obtained in good to high yields and enantiomeric ratios of up to 98:2 under mild and operationally simple reaction conditions.

A new enantioselective intramolecular strategy for the synthesis of enantioenriched bridged benzoxacines, unsaturated spirobenzofurans, 2,3‐dihydrobenzofuran and 2,3‐indoline acetate scaffolds in a tandem‐like diazotization/Heck‐Matsuda process directly from anilines has been developed. The process combines the in situ diazotization of the aniline, followed by the intramolecular Heck‐Matsuda reaction, thus skipping the isolation and purification of potentially unstable or hard‐to‐synthesize aryldiazonium salts. The practicality and robustness of the sequence were demonstrated by the synthesis of 30 complex motifs in yields up to 91% and enantiomeric ratios up to 97:3, including quaternary stereocenters. The in‐tandem processes from anilines were compared to conventional Heck‐Matsuda reactions using pre‐synthesized aryldiazonium salts. With few exceptions, the reactions starting directly from the anilines afforded better overall yields and enantioselectivity, demonstrating the efficiency of the method.

A new enantioselective intramolecular strategy for the synthesis of enantioenriched bridged benzoxacines, unsaturated spirobenzofurans, methyl-2,3-dihydrobenzofuran acetates, and methyl-2,3-indoline acetate scaffolds in a tandem-like diazotization/Heck Matsuda process directly from anilines has been developed. The process combines the in situ diazotization of the aniline, followed by the intramolecular Heck-Matsuda reaction, thus skipping the isolation and purification of unstable or hard-to-synthesize aryldiazonium salts. The practicality and robustness of the sequence were demonstrated by the synthesis of 26 examples of complex structural motifs with yields up to 91% and enantiomeric ratio (er) up to 97:3, including quaternary stereocenters. The in-tandem processes from anilines were compared to conventional Heck Matsuda reactions using pre-synthesized aryldiazonium salts. With few exceptions, the reactions starting directly from the anilines afforded better overall yields and er, demonstrating the efficiency of this method.