Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.



Ag2O-catalysed nucleophilic isocyanation: selective formation of less-stable benzylic isonitriles

Author affiliations

Abstract

Silver-catalysed benzylic isocyanation was achieved. When a readily available silver(I) compound, Ag2O, was employed as a catalyst in 1,4-dioxane, nucleophilic substitution of benzylic phosphates with trimethylsilyl cyanide (TMSCN) gave the less-stable benzylic isonitriles exclusively. No benzylic nitrile, which is the more stable regioisomer, was observed through the reaction. Notably, secondary benzylic isonitriles, which had not been available by catalytic substitutions, as well as primary ones were obtained in high yield. The selection of the leaving group of the benzylic electrophiles was crucially important, namely, the desired isonitriles were obtained in high yield only when the phosphates were used as substrates. A mechanistic study suggested that (TMS)[Ag(CN)2] formed in situ from the silver(I) salt and excess amounts of TMSCN functioned as an active species, and the substitution proceeded through an SN1-type process rather than in SN2 fashion.

Graphical abstract: Ag2O-catalysed nucleophilic isocyanation: selective formation of less-stable benzylic isonitriles

Back to tab navigation

Supplementary files

Article information


Submitted
16 Mar 2020
Accepted
26 Apr 2020
First published
27 Apr 2020

Org. Chem. Front., 2020, Advance Article
Article type
Research Article

Ag2O-catalysed nucleophilic isocyanation: selective formation of less-stable benzylic isonitriles

T. Yurino, Y. Tange, R. Tani and T. Ohkuma, Org. Chem. Front., 2020, Advance Article , DOI: 10.1039/D0QO00336K

Social activity

Search articles by author

Spotlight

Advertisements