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19.5.3.1.3 Method 3: Using Trimethylsilyl Cyanide

DOI: 10.1055/sos-SD-019-00079

Schmidt, A.Science of Synthesis, (200419136.

On heating heterocyclic N-oxides, such as pyridine,[‌17‌,‌18‌] quinoline,[‌17‌] pyrazine,[‌19‌,‌20‌] pyrimidine,[‌21‌] quinoxaline,[‌22‌] or isoquinoline N-oxides,[‌17‌] in the presence of triethylamine in acetonitrile or dimethylformamide with 34 equivalents of trimethylsilyl cyanide, the oxide is activated and the α-carbon atom is cyanated in a one-step procedure, for example, the formation of 9 in Scheme 5.[‌17‌] Alternatively, trimethylsilyl cyanide can be prepared in situ from sodium cyanide and chlorotrimethylsilane, e.g. formation of pyridine-2-carbonitriles 10 from pyridine 1-oxides[‌17‌] or 3-substituted pyrazine-2-carbonitriles 12 from pyridazine 1-oxides 11 (Scheme 5).[‌19‌,‌20‌]

Meeeee 8 Meeeeeeee ee Meeeeeee-8-eeeeeeeeeeeee eee 8-Meeeeeeeeee Meeeeeee-8-eeeeeeeeeeeee[‌88‌,‌88‌,‌88‌]

Meeeeeeeeee 8

M8 M8 M8 Meeee (%) Mee
M M M 88 [‌88‌]
Me M M 88 [‌88‌]
M M MM 88 [‌88‌]
M MM8M M 88 [‌88‌]

Me eeeeeeeeeee eeeeeeeee eeee eeeeeeeeeeeeee eeeeeee ee eeeeeeeeeeeeeee ee 8°M ee eee eeeeeeee ee eeeeeeeee eeeeeee ee eeeeeeeeeeeeeeeeee eeeeeeee.[‌88‌] Me eee eeeee, eeeeeeeeeeeeeeee ee eee eeeeeee eeeee. Meee eeeeee eeeee eeeeeeeeeeeeee eeeeeee ee ee eeeeeeeee ee ee eeeee eeeeeeeee eeee ee eeeeeee eeeeeeeeeeee M-eeeeee, eeee ee eeeeeeee ee eeeeeeeee 8-eeeeee, eeee eeeeeeee ee eeeeeeee-8- eee eeeeeeee-8-eeeeeeeeeeeee ee eeeeeeeeee ee eeeeeeeeee[‌88‌,‌88‌] ee eeeeeeeee[‌88‌] ee eee eeeeee eeee eee eeeeeeeeee eeeeeeeee eeee eeeeeee eeeeee eeeeeee.[‌88‌] Mee eeeeeeee ee e eee M-eeeeeeeeeeee eeeee eeeeee eeeeeeeeeeee eee eeee eeeeeeeeeeee. 8-(Meeeeeeeeee)eeeeeeeeee eeeee eeeeeee eeeeeeeeee eeee eeeeeee eeeeeeeee eeeeeee ee eeeee M8- eee M8-eeeeeeeeeee eeeeeeee eeee eeee ee eee eeeeeeeeeee eeeee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeee-8-eeeeeeeeeeee (8, M8=M):[‌88‌]

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

Meee eeeeeeeee ee eeeeeeee e eeee ee eeeeeee eeeeeeeee eeeeeeee 8-eeeee (8.88e, 88eeee) eee Me8M (8eM, 88.8eeee) ee eeeee MeMM (88eM) eee eeeeeee eeeeeeee eeee MMMMM (8.8eM, 88.8eeee) eeee e eeeeee ee 8e. Meee, eee eeee eee eeeeee ee 888°M (eee eeee) eee 88e. Meeee eeeeeee, eee eeeeeee eee eeeeeee eeee MM8Me8 eee ee MeMMM8. Mee eeeeeee eeeee eee eeeeeeeee eee eeeee (Me8MM8) ee eeeee e eeee eeeeeee eeeee eee eeeeeeeee eeee Me8M. Mee Me8M eee eeeeeeeeee eee eee eeeeeee eee eeeeeeeee ee e Meeeeeeee eeeeeeeee ee eeee eeeeeeee-8-eeeeeeeeeeee eee eeee eeee 8.8% ee eeeeeeee-8-eeeeeeeeeeee; eeeee: 8.88e (88%); ee 888888°M/88Meee.

8-Meeeeeeeeeeee-8-eeeeeeeeee Meee (88, M8=M8=M; M8=MM8M):[‌88‌]

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

M eeee ee eeeeeeee-8-eeeeeeeeee eeee 8-eeeee (8.88e, 88eeee), MeMM (8.88e, 88eeee), eee Me8M (88.8eM, 888eeee) ee eeeee MMM (888eM) eee eeeeee eeee MMMMe (88.8eM, 888eeee) ee 888888°M eee 88e. Meeee eeeeeeeeee eee eeeeeee ee eee eeeeeee, eee eeeee eeeeeee eee eeeeeeeee ee 8M MMe (888eM) eee eeeeeeeee eeee MM8Me8 (8×888eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeeeeeee, eee eee eeeeeee eee eeeeeeeee ee eee M8M (888eM), eeeeeee eeee eeeeeeee, eee eeeeeeee. Meeee eeeeeeeeeeeee, eee eeeeeee eeeeeeeeeeee ee eeeeeee eeeee; eeeee: 8.8e (88%). Mee eeeeeee eee eeeeeeeeeeeeee (M8M).

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