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DOI: 10.1055/sos-SD-019-00308

Suginome, M.; Ito, Y.Science of Synthesis, (200419446.

The reaction of silver cyanide with alkyl halides is the most significant milestone in the history of isocyanide chemistry, having led to the first recognition of isocyanides by Gautier and Hofmann in the mid-1860s (Scheme 3).[‌4‌‌8‌] Although it was believed that the yield cannot exceed 50%, on the basis of the amount of silver cyanide because of complexation of the isocyanide formed with the silver cyanide, it was later found that efficient stirring improved the yield to more than 50%. The method still requires an excess of potassium cyanide to liberate free isocyanides 2 from their complexes with silver iodide. A further modification to the procedure involves the use of the onium salts of dicyanoargentate [Ag(CN)2], which permits the convenient synthesis of benzylic isocyanides 3 from the corresponding halides.[‌9‌,‌10‌]

Meeeee 8 Meeeeeee ee Meeee Meeeeee eeee Meeeee Meeeeeee[‌8‌‌88‌]

Mee eeeeee eeeeeee eeeeee eee eeee eeeeeee ee eee eeeeeeeee ee eeee eeeeee eeeeeee ee eeeeeeeeeee eeee eee eeeeee eeeeeeeee ee eeeeeeeeee ee eeeee eeeee. Meeee eeeeeee M-eeee eeeeeeeeeee 8,[‌88‌] M-eeeeeee eeeeeeeeeee 8 (Meeeee 8),[‌88‌] eee α-eeeeeeeeeeeeee eeeeeeeeeee 8 (Meeeee 8).[‌88‌] Mee M-eeee eeeeeeeeeee 8 eee eeeeeeeeeee eeee eee eeeeeeeeeeeee eeee eeeeeee eee eeeeeeee ee eee-eeeeeeeeeee eeeeeeeeeee ee e eeee eeeeee: eeee eeeeeeeee eeeeee eee eeeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeee eeeeeeeeee 8 (M8=Me) ee 88% eeeee. Meeeeeee eee eeeeeeee eeeeeeeeee eee eeeee eee eeeeeee eeeee ee eeee eeeeee eeeeeeeee, ee ee eeeeeeeeeee eeee e eeeeee ee eee eeeeeee eeeee (88°M). Meeeeee eeeeeeeeee 8 (M8=Me) eeeeee eeee eeeeeeee ee eeee eeeeee eeeeeeee ee eeeeeeeeeee ee eee eeeeeeee eeeee; eeee ee ee eeeeeee eeee 8-eeeeeeeeeeeeeeeeeee, eeeeeee eeeeeeeeee 8 (M8=Me) eeeeeeeeee ee eeee eeeeeee eeeeeee. Mee M-eeeeeee eeeeeeeeeee 8 eee eeee eeeeee ee eeeeee eeeeeeee eeee eee eee M-eeee eeeeeeeeeee; eeeeeee, eeee eeeee eeeeeee eeeeeeeeee-ee-eeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeeee ee eeee eeeeeeeeeee. Mee eeeeeeee eeeeeeeeee 8 (M8=Me) ee eeeeeeee ee eee-eeeeeeeeeee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeee eeee eee ee eeeeee ee eeee eeeeeeeeeee eee e eee eeee eee eeeeeeeeeeee ee 88°M. α-Meeeeeeeeeeeee eeeeeeeeeee 8 eee eeeeeeeeeee ee eee eeeeeeee ee eeee eeeeeee eee eeeeeee ee eeeeeeeee eeee eeeeee eeeeeee. Meeeee, eeeeeee, ee eeeeeeee eeeeeee eee ee eeee eeee eeeeeee, eeeeeeeeeeeeee, eeeeeeeeeeee, eeeeeeeeeeee, ee eeeeeeeeeeee ee eee eeeeeeee eeeeeeeeee.

Meeeee 8 Meeeeeeee ee M-Meee Meeeeeeeeee eee M-Meeeeee Meeeeeeeeee[‌88‌,‌88‌]

Meeeee 8 Meeeeeeee ee α-Meeeeeeeeeee Meeeeeeeeee[‌88‌]

Meee eeeeeee eee eee eeeeeeeeeee ee eeee-eeeee eeeeeeeeeee eeeeeee eeeeeeeeeeeeee eeeeeee (Meeeee 8); eee eeeeeee, eee eeeeeeee ee eeeeeeeeeeeeee eeeeeee eeee eeeeeeeee eeeeeee ee eee eeeeeeee ee eeeeeeee(MM) eeeeeeee eeeee eee eeeeeeeeeeeee eeeeeeeeee 8 ee eeee eeeee.[‌88‌]

Meeeee 8 Meeeeeee ee Meee Meeeeeeee eeee Meeeeeeeeeeee Meeeeee ee eee Meeeeeee ee Meeeeeee(MM) Meeeeeee[‌88‌]

Mee eeeeee eeeeeeeeee ee eeeeeeee eeeeeeee eeee eeeeeeeeeee eee ee eeeeeeeeeeee ee eeeeeeeee eeee e eeeeeeeeeeeeee eeeeeee/eeee(MM) eeeeee/eeeeeeeeeeeeeeeeee eeeeeeee eeeeee (Meeeee 8).[‌88‌] Meee(MM) eeeeeee ee eeeeeeee eeeeeeee ee eeee(MM) eeeeee ee eeeee ee eee eeeeeeee eeeee. Meee eeeeeeee eeeeee eeee eeeeee ee eee eeee-eeeee eeeeeeeeeee 8; eee eeeeeee eeeeee eeeeeeee eeeeeeee eeee eeeeeeee eeeeeee eeeee eeeeeeee eeeeee eeeeeeeeee (eee Meeeee eeeeeeee) eeeeeeee ee eeeeeeeeeee ee eee eeeeeeeee eeeeeeeeee. Meeee eeeeeeeeeeee ee eeee-eeeee eeeeeeeeeee eeee eeeeeee eeeeeeeee ee e eeeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeee ee eee eeeeee ee Meeee eeeee.

Meeeee 8 Meeeeeeeee ee Meeeeeee Meeeeeee eeee eeee-Meeee Meeeeeeeeee ee eee Meeeeeeeeeeeee Meeeeee/Meee(MM) Meeeee/Meeeeeeeeeeeeeeeee Meeeeeee Meeeee[‌88‌]

Mee eeeeeeeeee ee eee eeeeeeeeeee, eeeee ee eeeeeeee ee eee eeeeeeee eeee ee eee eeeee eeeeeee, ee eeee eeeeeeeee eeeeeeee ee eee eeeeeeeeeeeeeee eeeeeeeee ee α-eeeeeeeeee-eeeeeeeeeee eeeee eeeeeeeeeee (Meeeee 8).[‌88‌] Meee, eeeeeeeeeeeeeee eeeeeeeee ee α-eeeeeeeeee-eeeeeeeeeee eeeeeeeee eeeeeeeee 8 ee eee eeeeeeee ee eeeeeeeeeeeeee eeeeeee eeeee ee eeeeeeeee eeeeeeeee ee eee eeeeeeeeeeeee α-eeeeeeeeee-eeeeeeeeeee eeeee eeeeeeeeeee 88 ee e eeeeeeeeeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee ee eee eeeeeeee eeeeee. Meeeeeeeeeeee, eeeeeeeee eeeeeeeee ee eee eeeeeee 88 ee eeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeeeeeee/eeeeeeeeeeeeeee. Me ee eeeeeeee eeee eee eeeeeee ee eeeeee ee eeeeeeeeee/eeeeeee eeeeeeeeeeeee[‌88‌‌88‌] (eee Meeeeee eeeeeeeee ee ee eeeeeeeeeeeeeeee eeee.

Meeeee 8 Meeeeeeee ee α-Meeeeeeeee-Meeeeeeeeee Meeeeeeeeee ee Meeeeeeeeeeeeee Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeee Meeeeeeeee (8, M8=Me); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeeee eeee (Meeeeee; MeMeeeee, Meeeeee Meeeeeeee, Meeeeeeeee Meeeee MM), Meeeeeeee (8888), e888, eeee eeeeeeeeee eeee Meee Meeee&Meee, Mee.

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

MeMM (888e, 8.88eee) eee eeeee eeee eeeeeeee ee MeM (888e, 8.8eee) ee ee ee e eeeee eeeeeeee eeee e eeeeeeeeee eeeeeee. Mee eeeee eeeee ee eee eeeee eee eeeeeeee ee e eeeee eeee eee eee eeeeeee eee eeeeeee eeeeeeeeee eeeee ee eeeeee eeee e eeeeeee, eeeeeeeeeee, eeeee eeeeee (8e). Meeeeeee eee eeeeeeeeeee, eee eeeee eeee eee eeeeeee, eee eee eeeeeee eee eeeeee ee e eeeeeeee eeee eeeee eee eeeeee. M8M (888eM) eee eeeee eeeeeee eee eeeeeeeee. MMM (888e, 8.88eee) eee M8M (888eM) eeee eeee eeeee eeeeeee eee eeeee eeee ee eee eeeee, eee eee eeeeeee eee eeeeeee eee eeeee 88eee, eeeeee eeeee eeee eee eeeee eeeee eeeeee eeeee eee eeeeeee eeee eeeeeeeeeee eee e eeeee eeeee ee MeMM eeeeeeee eeeee eee eeeeeee eeee. Mee eee-eeeeeee eeeeeeeeee eee eeeeeeeee eeeeeeee eeee eee eeeeeeee eeeee ee eeee e eeeee eeeeeeeeee, eee eeeeeee eeeeeee ee eeeee eee eeeeeeeeeee ee 8888°M/888Meee; eeeee: 88888e (8888%).

Meeeeeeeeeeeee Meeeeeeeee (8, M8=MMMe8); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

Me8MMe(MM)8 (M=MMe8; 8e, 88eeee), eeeeeeee eeee Me8MMe (88eeee) eee MeMM (88eeee) ee MeMM (888eM), eee eeeee ee e eeee ee MeMM (888eM) ee Me8MMMe (8.8e, 88eeee), eeeeeeeeeeeeee eeee MeMM. Mee eeeeeee eee eeeeeee eee 88e ee 88°M eeee eeeeeeee eee eee eeeeeee eeeeeeeeee ee eeeee. Mee eeeeeee eee eeeee ee ee Me8M eee eeeeeeeeeeeeee (eeeeeeeee eeeee); eeeee: 8.8e (eeeee).

Meeeeee Meeeeeeeee (8, M8=Me); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

MeMM eee eeeeeeeeeeee ee eeeeee ee eeeee ee MeMM8 eee MMM, eeeeee eeee MeMM eee Me8M eeeeeee eeeeeeee, eee eeeee ee 888°M eeee M8M8. MeM (8.8e, 8.8eeee) eee eeeee ee e eeee ee eee MeMM (8.8e, 88.8eeee) ee eeeee MM8Me8 (88eM), eee eee eeeeeee eee eeeeeee eee 88eee ee 88°M. Mee Me eeeee eeee eeeeeee eeeeeeeee eee eee eeeeeee eee eeeeeee ee eeeeeeeeeee ee 88°M/8.8Meee. Meeeeeeeeee ee eee eeeeeee ee 8°M/8×888Meee eeee eee eeeee eeeeeeeeee, eeeee eee eeeeeeeee ee e eeee eeeeee eeeeee eeee eee M8; eeeee: 8.88e (88%); ee 88°M.

α-Meeeeeeeeeee Meeeeeeeeee 8; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

Me eeee eeeeeee (88eeee) eee eeeee ee e eeeeeeeeee ee MeMM (88eeee) ee e eeeeee (888eeee) eeeee eee-eeeeeee eeee eeeeeeee. Meeee 88eee, eee eee eeee eee eeeeeee eee eeeeeeee eee eeeeeeeee eee 88e. Meeeeeeeeeee, eee eeeeee eeeeee eee eeeeeee ee eeeee. MMMe8 eee 88% ee MMM eeee eeeee eeeee eee eeeee eeeeeeeee. Mee eeeeeee eeeee eee eeeee (MeMM8) eee eee eeeeeee eee eeeeeee ee eeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeee ee ee eeeeeeeeeeeeeeeee (eeeeeeeee eeeee).

8-Meeeeeeee Meeeeeeeee (8); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

Me e eeee ee 8-eeeeeeeeeeeeeeee (888ee, 8.8eeee) eee MeMe8 (888ee, 8eeee) ee MM8Me8 (8eM) eee eeeee MMMMM (888ee, 8.8eeee) ee MM8Me8 (8eM) ee 8°M, eee eee eeeeeee eee eeeeeee eee 888eee ee eeee eeeeeeeeeee. Meeeeeeeeee ee eee eeeeeee ee eeeee eeee e eeeeee eeeeeee ee eeeee eeeeeeee (8.8eM) ee Me8M (8eM) eee eeeee. Meeee eeeeeeeee, eee eeeeeee eee eeeee eeeeeeeeee, eee eee eeeeeee eee eeeeeeeee eeee eeeeee. Meeeeeeeeeeee ee eee eeee eeee eee eeeeeeeeee ee e eeeee eeeeeeeeeee eeeee; eeeee: 888ee (88%).

Meeeeeee Meeee Meeeeeeeeee 8 eeee Meeeeeee Meeeeeee; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

MMMMM (8.8eeee) eee eeeee ee e eeee ee e eeeeeeee eeeeeee (8.8eeee) eee e eeee eeeeee (8.8eeee) ee eee MM8Me8 (8eM) eeeee eeeee. Mee eeeeeee eee eeeeeee ee ee eee 88e eee eeee 8.8M eeee ee Me8MM ee MMM (8.8eM, 8.8eeee) eee eeeee. Mee eeeeeee eee eeeeeee eee ee eeeeeeeeee 88eee, eeee eeeeee eeee eee. ee MeMMM8 eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee M8M eee eeeee eee eeee eeeee (MeMM8). Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).