In-situ Utilization of Non-Stabilized Diazoalkanes from (3+2) Cycloaddition of Linear N,N-Disilyl Enamines and Azides

A (3+2) cycloaddition reaction of linear N,N-disilyl enamines and organic azides is investigated. The N,N-disilyl enamines, derived from the selective double hydrosilylation of conjugated nitriles, are employed in-situ for this investigation. The resulting triazoline intermediate from the (3+2) cycloaddition reaction promptly undergoes retro-(3+2) cycloaddition to yield versatile non-stabilized diazoalkane, along with formamidine. The presence of a transient and unstable alkyl diazomethane is confirmed by utilizing carboxylates as trapping reagents. Furthermore, we demonstrate the versatility of these alkyl diazomethanes by utilizing them in reactions with various reagents, including hydroborane, diboron, silaborane, alkenes, and alkynes.

Automated summary

This study investigates a (3+2) cycloaddition reaction between linear N,N-disilyl enamines and organic azides. The N,N-disilyl enamines, obtained from the selective double hydrosilylation of conjugated nitriles, are used in-situ for this reaction. The resulting triazoline intermediate promptly undergoes retro-(3+2) cycloaddition to yield versatile non-stabilized diazoalkane and formamidine. The presence of transient and unstable alkyl diazomethane is confirmed by utilizing carboxylates as trapping reagents. Furthermore, the versatility of these alkyl diazomethanes is demonstrated in reactions with various reagents, including hydroborane, diboron, silaborane, alkenes, and alkynes.