125038-93-9

Upstream product

• 2556-73-2 1-methyl-2-azepanone 
• 536-74-3 phenylacetylene 
• 25355-42-4 2-Methylmercapto-1-methyl-Δ¹-tetrahydroazepinium-iodid 
• 34949-15-0 Hexahydro-1-methyl-2H-azepine-2-thione 

Relevant academic research and scientific papers

First synthesis of medium-sized ring allenyl lactams

Medium-sized lactams bearing an axially chiral allene unit have been synthesized by using an aza-ketene Claisen rearrangement. Starting from 2-alkynylpiperidines or 2-alkynylazepines, ring enlargement enabled the highly diastereoselective formation of 10-

Aromatic Aza-Claisen Rearrangement of Arylpropargylammonium Salts Generated in situ from Arynes and Tertiary Propargylamines

The charge-accelerated aza-Claisen rearrangement of ammonium salts serves as a key step in the construction of complex nitrogen-containing molecules. However, much less attention has been paid to the aromatic aza-Claisen rearrangement than to the aliphatic one. Herein, we report an unprecedented aromatic aza-Claisen rearrangement of arylpropargylammonium salts, generated in situ from arynes and tertiary propargylamines, delivering structurally diverse 2-propargylanilines in moderate to good yields with high regioselectivity. This rearrangement proceeds in the absence of strong bases or transition metals, is compatible with moisture and air, tolerates a wide variety of functional groups, and is amenable to forming 11- to 13-membered heterocycles with a triple bond. The 2-propargylaniline products were treated with aluminum chloride in ethanol to afford multisubstituted indoles in moderate to excellent yields. Finally, a series of deuterium-labeling experiments was performed to elucidate the reaction mechanism.

Alkynylation of Thiolactams. New Synthesis of α-Substituted Pyrrolidine and Piperidine Alkaloids

Alkynylation of S-alkylthioamidium salts of thiolactams with lithium acetylides followed by reduction with LiAlH4 provided α-alkynylazacycloalkanes, which on reduction, or hydroboration followed by oxidation, gave α-substituted pyrrolidine and piperidine alkaloids.