Regioselective [3 + 2] Annulation of Multisubstituted N-Allenamides: A Palladium-Catalyzed Heck/Tsuji-Trost Cascade
Yuxin Wen1, Linghui Meng1, Yu Song1
1School of Chemistry and Materials, Yangzhou University, Yangzhou, Jiangsu 225002, China.
Abstract:
A palladium-catalyzed Heck/Tsuji-Trost cascade has been established for the regioselective [3 + 2] annulation of multisubstituted N-allenamides with ortho-iodoaniline and ortho-iodophenol derivatives. Notably, this approach proceeds via selective γ-attack on multisubstituted N-allenamides, delivering distal bond insertion products, in contrast to previously reported reactions involving proximal bond insertion of simple N-allenamides. This method enables the efficient synthesis of enamide-tagged indolines and dihydrobenzofurans bearing quaternary carbon centers in good to excellent yields with exclusive distal regioselectivity and broad functional group compatibility. Density functional theory calculations provide a clear rationale for the observed regio- and geometric selectivity.
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