Isopropyl

Pathology

Medicinal chemistry

Catalysis

Organic chemistry

Nucleophile

Chemistry

Indole test

Alternative medicine

Combinatorial chemistry

Cycloisomerization

Reactivity (psychology)

Alkyne

Alkyl

Propargyl

Regioselectivity

Stereochemistry

Medicine

Intramolecular force

Umpolung

Sulfonyl

Angewandte Chemie International Edition

A regioselective sulfonyl/sulfinyl migration cycloisomerization cascade of alkyne-tethered ynamides is developed in the presence of XPhosgold catalyst. This reaction is the first example of a general [1,3]-sulfonyl migration from the nitrogen center to the β-carbon atom of ynamides, followed by umpolung 5-endo-dig cyclization of the ynamide α-carbon atom to the gold-activated alkyne, and final deaurative [1,5]-sulfinylation. This process allows the synthesis of peripherally decorated unconventional 4-sulfinylated pyrroles with broad scope from N-propargyl-tethered ynamides. In contrast, N-homopropargyl-tethered ynamides undergo intramolecular tetradehydro Diels-Alder reaction to provide 2,3-dihydro-benzo[f]indole derivatives. Control experiments and density-functional theory studies were used to study the reaction pathways.

Umpolung Reactivity of Ynamides: An Unconventional [1,3]‐Sulfonyl and [1,5]‐Sulfinyl Migration Cascade