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Please login to access the full content or check if you have access via Variation 3: By Palladium- and Nickel-Catalyzed Substitutions

DOI: 10.1055/sos-SD-019-00127

Subramanian, L. R.Science of Synthesis, (200419184.

It is possible to supersede the use of copper(I) cyanide and substitute it with alkali cyanides, zinc(II) cyanide, or other reagents such as trimethylsilyl cyanide by carrying out the cyanation reaction of aryl halides in the presence of a palladium catalyst under milder conditions. Since earlier reports, several variations of this method with improved yields and ease of manipulation have been published.[‌49‌‌52‌] Aryl bromides are usually used as starting materials, although they are less reactive than the iodides.[‌53‌]

Meeee eeeee eeeeeeee eeee eeeeeeee eeeeeeee ee eeee eeeeeee eeeee eeeee eeee MM eeee eeeeeeeee eee eeeeeeee. Me eeeeeee eeeeeeee eee eeeee eeeeeee, eeeeeeeee eee eeee, eee eeeeeeeeeeeeeeeeee. Meee eeeee-eeeeeeeeeeeee eeee eeeeeeee eeeeee eeee eeeeee ee eee eeeeeeeee eeeeeee.[‌88‌] Meeeeeeee eeeeeeeeeee eeeeeee eeee eeee eeeeeeeee, eeee eeee ee eee eeeeee eeeeeeeeee ee 8MMMM eeeeeeeeeeee. Mee eeeeeeee eeeee ee eeeeeee 88 eeee 8-eeeee-8,8-eeeeeeeeeeeeeee (88) ee 88% eeeee eeeeeeeeeeee ee eee eeeeeee eee eeeee eeeeeeee, eee eeeeee eeeeee eeeeeeeee eeeeeeeee ee eeeeeee (Meeeee 88).

Meeeee 88 Meeee Meeee Meeeeeee eeee Meeeeeee ee ee Meee Meeeee[‌88‌]

Meeeeeeeeeeee ee eee eeeeeee ee eeeeee eee eeeeeeeee-eeeeeeeee eeeee eeeeeeee eeee eeeeeeeeeeeeee eeeeeee. Mee eeeeeeee eeeeeeee eeeee eeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee(8) ee eeeeeeeeeee eeee eee eee eeeeeeeeee ee eeee eeeeeee 88 eeee eeeeeeee 88.[‌88‌] Meeeeeeee eee eeeeeeee ee eee eeeee. Meeeeeeeeeeee eeee eeeeeeee eee eeeeeeeeeeeeeeeeeee eeeeeeeee, eeeee eee eeeeeeeee eeeeeeeeee eee eeeee ee eeeee eeeeeeeeeeee eeeeeee ee eee eeeeeeee (Meeeee 88).

Mee eeeeeee ee eeeeeeeeeee eeeeeee ee eeeeeeeee-eeeeeeeee eeeeeeeee eeeeee eeee eeeeeee eeee eeeeeeeeee eeee eeeeeeeee(MM) eee eeeeeeeee(8) ee eee eeeeeeeee eeeee.[‌88‌,‌88‌] Meeeeee, eeeee eeeee eeeeeeeee {eeeee-eeeee[8-(eeeeeeeeeeeeeee)eeeeee]eee(eeeeeeeeeeeeeeeeee)eeeeeeeee(MM) ee eee eeeee eeeeeeee} ee eee eeeeeeee ee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee (eeeee), eeee eeeeee ee eeeeeeeeeeeeee eeeeeee eeee eee eeeeeeee eeeeee eeeeeeeeee M,M,M,M-eeeeeeeeeeeeeeeeeeeeeeeeee eeeeee eee eeeeeeeeee ee eeee eeeeeeee 88 eeee eeee eeeeeeee 88.[‌88‌] Meee eeeeee eeeeeeee ee eee eeeeeeeeeeeeee, eee eee eeeeeeee eeeeee, eee eeeeeeeee eee eeee eeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee ee Meee Meeeeeee eee Meeeeee eeee Meeeeeeeeeeeee Meeeeee[‌88‌,‌88‌]

Meeeeeeee, eeee eeeeeeeee eeeeee ee 8-eeeeeee-8-eeeeeeeeeeeeeeeeeeee (eeeeeee eeeeeeeeeee) eeee eeee eeeeeeeeee ee eeee eeeeeeee eee eeeeeeeee 88 eeee eeee eeeeeeee 88 eeeee eeeeeeeee-eeeeeeeee eeeeeeeeee, eeeee eeeee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee (eeeee).[‌88‌] Meee eeee eeeeeeeeee eeeee eee eeeeee (ee MM) eeee eeee eeeeeeee eee eeee eeeeee (Meeeee 88).

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee ee Meee Meeeeee ee eee Meeeeeee ee Meeeeee Meeeeeeeeee[‌88‌]

Mee eeeeeeeeeeeee ee eeee eeeeeee eeee ee eee eeeeeeee eeeeee ee eeeeeeeeeeeee eeeee eeee eeee(MM) eeeeeee, eeeee ee eeeeee eeeeeeee ee eeeeee eeeeeeee eeee eeeeee eee eeeeeeeee eeeeeee. Mee eeeeeeeeee ee eeee(MM) eeeeeee ee eeeeeeeeeeeeeeeee ee 88°M ee eee (8.8×888 ee. 8.8×888 eee eeeeee eeeeeee eee 8.8×888 eeeeeeeee eeeeeee) eee ee ee eeeeeeeeee, eeeeee e eeeeeee eeeeeee eeeeee ee eee eeeeeeeee eeeee, eee eee eeeeeeeeeeeeee ee eeee eeeeeee eeee eeee eeeeeeee.[‌88‌] Me eeee eee e 88% eeeee ee eeee eeeeeee 88 ee eeeeeeee eeee eeee eeeeeee 88 (Meeeee 88).[‌88‌,‌88‌] M eeeeeee eeeeeeeee eeeee ee eeee eeeeee eee eeeeeeeeee eeee eeeeeee 88 eeee eeeeeeee 88 ee eeeeeeeee eeeee eee eeee eeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeeee ee Meeeeeeeeeee Meeeeeeeeee Meee Meeeeee eeee Meee Meeeeeee eeee Meee(MM) Meeeeee[‌88‌,‌88‌]

Meeeeeee eeee eeeeeeee, eee eeeeeee eeeeeeeee eeee eeeeeeeee 88 eee ee eeeeeeeeeeee eeeeeeeeeee eeee eeee eeeeeeee 88 ee eeee eeee eeeeee ee eeeeeeeee-eeeeeeeee eeeeeeeee eeee eeee(MM) eeeeeee ee eee eeeeeeee ee e eeeeeeeee eeeeee ee eeee eeeeee[‌88‌] ee eeeeeeeeeeeeeeeee.[‌88‌,‌88‌] Meee eeeeeeee-eeeeeeeee eee eeeeeeee-eeee eeee eeeeeeeee eee eeeeeeeeeee eeeeeeee eeeee eeeee eeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeeee ee Meee Meeeeeeee eeee Meee Meeeeeee eeee Meee(MM) Meeeeee ee eee Meeeeeee ee Meee Meeeee[‌88‌]

Mee eeeeee ee eee eeeeeeeee eeeeeeee, eeeeee, eee eeeeeee eeee e eeeeeeeeee eeee ee eee eeeeeeeee ee eeee eeeeeee. Meeee eeeeeeeeee eeeeeee eeee eeeeeee eeeeeeeee eeeeeeeee eee eeeeeee, e eeeeeeeee eeeeeeeeeeeeeeeeeeee eeeeeeee [Me8(eee)8] eee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeeeee ee eee eeeeee eeeeeeee eeee eeeeeeeeee ee e eeeeeee eeeeeee (Meeeeee ee eee eeeeeeeeeeeeeeeee. Mee eeeeeeeee eeee eeeee eeee eeeeeee eeee eeee eeeeeeee 88 eeeeee eeee eeeeeeee 88 eee eeee eee eeeeeee eee eeeeeeee ee eeee eeeeee (Meeeee 88);[‌88‌] eeee eeeeeeeee-eeeeeeeee eeeeeeeee eeee eeee(MM) eeeeeee eee eeee eeee eeeeeeee ee eeeee eeee(MM) eeeeeee[‌88‌] ee eeee ee eeee eeeeee.[‌88‌] Meee(MM) eeeeeee eeeeeee eeee eeeeeeeee eeeeeeee ee eeeeeeeee ee eeeeeee eee eeeeeeee eeeeee ee eee eeeeeeeee eeeee. Meeeeee eeeeeeeee ee eeee eee eeeeeeee eee ee eeeeeee eee ee eeee eeeeeee eee eee ee eeeeee eeeeeee, ee ee eee eeee eee eeeeeeeee eeeee eeee eeee eeeeee. Meeeeee, eeee eeeeeeeee eee eeeeeeee eeee 8-eeeee eee 8-eeeee eeeeeeeeeeee ee eee eeeeeee eeeeeeeeeee eeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee ee Meee Meeeeeee eeee Meee(MM) Meeeeee ee Mee Meeeeeeeeeeeeeeee[‌88‌,‌88‌]

Meeeee(M) eeeeeee eee eeee ee eeee ee eee eeeeeeeee eeeee ee eeeeeeeee-eeeeeeeee eeeeeeeee, eee eeee eeeeee eee eee ee 8,8-eeeeeee ee eeeeeee. Mee eeee eeeeee eeeeeeeee eeeeeeeeeeeeeeeeeeee eeeeeeee [Me8(eee)8] ee eeee ee eee eeeeeeee ee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeeeee ee eeeeee eee eeeeeeeeeeeeeeeeee eeeeeee ee ee eeeeeeee. Meee eeee eeeeeeee eee eeeeeee 88 eee eeeeeeeee eeee eee eeeeeeeeeeeee eeeeeeee 88 eeeee eeee eeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee ee Meee Meeeeee eeee Meeeee(M) Meeeeee[‌88‌]

Meee eeeeee ee eeeeeeeeee eee eeee eeee ee eee eeeeeeeee ee eeee eeeeeee 88 ee eeeeeeee 88 eeee eeeeee eeeeeee, eeeeeeeee ee eeeeeee eeeeeeeee eeeeeeeee ee eeeeeeeee {e.e., MeMe8[MMe8(ee-8)]8} ee eeeeeee (Meeeee 88).[‌88‌] Mee eeeeeeee ee eeeeeee eee ee e eeeeeeeeeee eee-eeeee eeeeee. Mee eeee eeeeee ee eeeeee ee eeeeee eee eeeeeeeee eeeeeee ee eee eeeeeeeeeeeee eeeeee eeeeeee ee eeeeeeee eeeeeee,[‌88‌] ee eeeee ee eee eeee eeee eee eeeeeeee eeee eeeeeeee eeeee e eeeeeeeee eeeeeee ee eee eeeee eeeeeeeee eeeee {MeMeMe[MMe8(ee-8)]8} eeeeeee eeee eeeeee. Mee eeee eeeeeeeeee ee eee eeeeeee eeeeeeeee ee eeeeeeeeee ee e eeeeeeeee eeeeee, ee ee eeeeee eeeeeeeee. Meee, eee eeeeeeeeeeeeee eeeeeeeeeeee ee eee eeeeeeeee eeeeeee eeee eee eeeeeee eeeee eeee eee eeee eeeee eee ee eeee eeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeee eeeeeeee ee eee eeeee eeeeeeeee eeeeee. Meeeee eee eeeeeeeeeeeeee eeeeee eee eeeeeeee, eee ee eee eeeee eee eeeeeeee eeeeee eee 88 eee 88%.

Meeeeee eeeee-eeeeeee eeeeeeee {MeMe8[MMe8(ee)]8} eee ee eeee eeeeeeeeeee ee eee eeeeeeeee ee eeee eeeeeee 88 eeee eeeeee eeeeeee eeeee eeeeeeeeeeee eee-eeeee eeeeeeeeee ee eee eeeeeeee ee eeee(MM) eeeeeeee eee eeeeee eeeeeeeeeee (Meeeee 88).[‌88‌] Meee eeeeeeee eeeeeeeee eee eee eeeeeeeee ee eeee eeeeeeeeee ee eee eeeeeee 88 eeee eee eeeeeee ee eeeeeeee eee eeeeeeee. Mee eeeeee eeeeeeeee eeeeeeee ee eee eeeeeeee eeeeeee eeeeeee ee eeeeeeeeeeeeee ee eeeeeee-eeeee eeeeeeeee.[‌88‌] Mee eeeeeeeee ee eeeeeeeee eeeeeeeeee ee ee e eeeeeee eeeee eeeeeeee eeeeeeee, ee eeeee eee eeeeeeeeeee eeeeeeeee eeeeeee eeeeeeeeee eee eeee eeeeee 88 eeee eee eeeeeee eeeee eeee eee eeeeeee eeeee eee eeeeeeeee eee eeeeeeee, eeee eee eeeeeee eeeeee eeeeeeeee ee eee eeeeeee eeeee. Mee eeeeeeeee eeee eee eeeeeee ee eee eeeeeee ee eeee(MM) eeeeeeee, eeeee ee eeeeee ee eeeeeee eee eeeeeeeeeeee ee eee eeeee-eeeeeee eeeeeeee ee ee eeeeee ee eee eeeeeee eee. Meeeee eeeeeeeeeee ee eeee eeeeeeeee eee eeeeeeee, eeeeeeeeee eeee eee eeeeeeeeeeeee eeeeee eeeeeee ee eeeeeeee e eeeeeeeeee eeeeeeeee eeeeeee. Meee eeeeeeee eeee eeeeeeee-eeeeeeeeeee eeeeeeeeeeee eeee eeee eeeeee (ee MM) eeeee eeeee eeeeeeeeee, eeeeeee eeeee- eee eeeeeeeeeeeee eeeee ee ee eeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee ee Meee Meeeeee eeee Meeeee Meeeeee ee Mee-Meeee Meeeeee[‌88‌,‌88‌]

Meeeeeeeeeeeee eeeeeee ee eeee ee eeeeee eeeee eee ee eeeeeee ee eeeee e eeeeeeeeeee ee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee (eeeee) ee e eeeeee eee M,M,M,M-eeeeeeeeeeeeeeeeeeeeeeeeee ee eeeeeeeeee ee eee eeeeee eeeeeeeee-eeeeeeeee eeeeeeeee ee eeeeeeeee eeee eeeeeeeee 88 eeee eeeeeeeee eeeeeee (Meeeee 88; eeeeee ee MM). Me eeeeeeeee ee eeee eeeeee eeee eeeeeee eeeeeeeeee, 8,8-eeeeeeeeeeeeeeeeeeeee (MMM) eeeeeeee eee eeeeee ee eeeeeeee 88 eeee eeeeeeeeeeee eeee eeeeeeeee 88 (Meeeee 88).[‌88‌,‌88‌] Mee eeeee eeeeeeeeee eeeeeeee eeeeeeeeeeee ee eeeeeeeee(8) eeeeeeeee eeeeee ee eeeeeee eeee eee eeeeeeeee eee eeeeeeeee ee eee eeeeeeeee eeeeee. Mee eeeeee eeeeeeeee eeee eeeeeeeee eeeeeee eee eeeeee eeeeeeeee eeeeeee; eeeeee eee eeeee eeeeeeeeee ee eee eeeeeeeeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeeeeee ee Meee Meeeeeeee eeee Meeeeeeee Meeeeee[‌88‌,‌88‌]

Meeeeeeee-eeeeeeeee eeeeeeeee eee eeeeee eeeeeeeeee eee eeeeeeeee eee eee eeeeeee eeeee ee 8,8,8,8,88,88-eeeeeeeeeeeeeeeeeeeee (88) ee eeee eeeeeeeeeeee-8,8,8,8,88,88-eeeeeeeeeeeeeeee (88). Mee eeeeeeee eeeeeeee eeee eeeeeeeee eeeeeee ee 8-eeeeeeeeeeeeeeeee ee 888°M ee eee eeeeeeee ee eeeeeee-88-eeeee-8 eee eeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee(8) ee eeeeeeee (Meeeee 88).[‌88‌] Mee eeeeeeee ee eeeeeee eeee eeeeee(M) eeeeeee eee eee eeee eeeeeeee eeeee eee Meeeeeeeeeee Meeee eeeeeeee eeeee eeee ee eeeeeee eeeeeeeee.[‌88‌]

Meeeee 88 Meeeeeeee ee Meeeeeeeeeee-8,8,8,8,88,88-eeeeeeeeeeeeeeee[‌88‌]

Meeeeeee eeeeeeeee eee eeee eeee eeeeeee ee eee eeeeeeee ee eee eeeeeeeee ee eeee eeeeeee eee ee eee eeee eeeeeeeee eeee eeeee, e eee eeeeeee ee eeeeee ee eeeeeeee ee eeeee eeeeeeeee eeeee ee eee eeeeeeeeee. Meeeeee eeee eeeeeee ee eee eeeeee-eeeeeeeee eeeeeeeee ee eeeeee eeee eeeeeeeee ee eeee eeeeeeee eeeeeeeeeeeeee eeee eeeeeeeeeeeeeeeeeeee eeeeeeee ee eee eeeeeee; eeeeeee, ee eee eeee ee eeeeeee, eeee eeeeeee ee e eeeeeeee eeeeeeeeee. Mee eeeeeeeee ee eeee eeeeeeeee 88 ee eeeeeeeee eeee (eeeeeeeeeeeeeeeeee)eeeeee [Me(MMe8)e], eeeeeeeee ee eeee eeee e eeeeeeeeee eeeeeee [MeMe8(MMe8)8MeMMe8].[‌88‌] Meeeeeeee eeeeeeee eeeeeeee ee eeeeee eeeeee eee eeeeeeeee eeee eee eeeeeeee eeeeee eeeeeee eeeeeeeeeeee eeee eeeeeee eeeeee eeeee eeeeeee (MMM, MeMM)eeeeeee eeeeeee eeeeeee eeeeeee (eeeeeeeeee MMMM) eeee eee eeeeeee eeeeeeeeee eee eeee (Meeeee 88). Meeee eee eeeeeeee eeeeeeeee eeee, 8-eeeeee-, 8-eeeee-, eee 8-eeeee-eeeeeeeeeeeeee eeee eeee eeeeee ee eeeeeeee 88.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeee ee Meee Meeeeeeee eeee Meeeeeeee Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meee Meeeeeee 88 eeee Meee Meeeeeee 88 (M=Me); Meeeeee Meeeeeeee:[‌88‌]

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

Meee eeeeeee 88 (88eeee) eee eeeeeeee eeee Me(MM)8 (8.8eeee) eee Me(MMe8)8 (8.88eeee) ee eeeeeeeeeeee MMM (88eM), eee eee eeeeee eeeeee eee eeeeee ee 88°M eeeee M8 eeeee MMMM eeeeee eee eeeeeee ee eeeeeeee eeeeeeee (88e). Mee eeeeeee eee eeeeee ee ee eee eeeeeee eeee eeeeeee (88eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (88eM) eee eeeeeeeeeeee ee eeeee ee eeee eee eeeeeee eeeee eee eeeeeeeee >88% eeee.

Meee Meeeeeee 88 eeee Meee Meeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

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

Meee eeeeeeee 88 (8.8eeee), Me8(eee)8 (88ee, 8.88eeee), eeee (88ee, 8.88eeee), Me eeeeee (88ee, 8.88eeee), eee Me(MM)8 (888ee, 8.8eeee) eeee eeeeee ee e eeeee eeeee eee eeeeeee eeee M8. MMM (8eM) eee eeeee eee eeeeeee. Mee eeeeeeeee eeeeeee eee eeeeee ee 888°M eeeee M8 eeee eeeeeeee eeeeeeeee eeeee MMM eeeeee eee eeeeeeeeeeeee ee eeeeeeee eeeeeeee (ee. 8.8888e). Mee eeeeeee eee eeeeee ee ee, eeeeeee eeee MeMMe (88eM), eee eee MeMMe eeeee eee eeeeee eeee 8M MM8MM eeee eeeeeeee ee eeeee. Meeee eeeeee (Me8MM8), eee MeMMe eeee eee eeeeeeeeeeee ee eeeeee eeeeeeeeeee. Mee eeeeeee eee eeeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee) ee eeee eee eeee eeeeeee.

Meeeeeeeeeee-8,8,8,8,88,88-eeeeeeeeeeeeeeee (88):[‌88‌]

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

Me e eeee ee 8,8,8,8,88,88-eeeeeeeeeeeeeeeeeeeee (88; 8e, 8.8eeee) ee 8-eeeeeeeeeeeeeeeee (88eM) eee eeeee MMM (8.88e, 8.8eeee), eeeeeee-88-eeeee-8 (8.88e, 8eeee), eee Me(MMe8)8 (8.8e, 8eeee) eeeee M8. Mee eeeeeee eee eeeeee eee 88e ee 888°M, eeeeee ee 88°M, eeeeeee eeee e eeeeeee ee eeee eeeeeee/eeeeeee (8:8), eee eeeeeeee ee eeee eeeeeeeeeee. Mee eeeeeee eee eeeeee eeee eeeeeee eee eeee eeeee eeeeeee ee Me8M eee MeMM. Meeeee MMM eee eeeee eeeee eeee eeeeeee ee eeeeeee eeee M8M (8888eM) eee eeeeee. Me eeeeee eee Me8M eee eee eeeee eeeee, eee eeeeeee eee eeeeeeeee eee 88e ee e Meeeeee eeeeeeeee (Me8M). Mee eeeeeee eee eeeeeee ee eeee e eeeee eeeee; eeeee: 888ee (88%).