Science of Synthesis

Podlech, J., Science of Synthesis, (2004) 19, 334.

The hydrocyanation of aliphatic alkenes with nickel–phosphite catalysts usually requires the addition of a Lewis acid such as zinc(II) chloride, aluminum trichloride, or a borane (catalyst/Lewis acid 1:1) and tends to give the anti-Markovnikov products ‌1‌ rather than the branched nitriles ‌2‌ (‌Scheme 2‌).[‌6‌,‌35‌–‌38‌] As the Lewis acids are often responsible for a preceding isomerization of the alkene, mixtures of isomeric alkenes can be employed to give a single product.[‌5‌,‌39‌,‌40‌] The nickel-catalyzed hydrocyanation of isolated alkenes is much faster for terminal alkenes than internal alkenes. The mode of addition for the hydrogen cyanide is crucial in this reaction: it is mandatory to maintain a low hydrogen cyanide concentration by slow addition, since a second equivalent of hydrogen cyanide adds oxidatively to zerovalent nickel in an irreversible reaction, resulting in loss of catalytic activity.[‌21‌,‌41‌] This oxidative addition seems to be enhanced by most Lewis acids, but is prevented when triphenylborane is used.[‌29‌]

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Meeeeeeeeeeeee (‌8‌, M8 = Me; e = 8) eee 8-Meeeeeeeeeeeeeeeeee (‌8‌, M8 = Me; e = 8); Meeeeee Meeeeeeee:[‌88‌]

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Me[M(M-8-Mee)8]8 (8.8 e, 8 eeee), MeMe8 (8.88 e, 8 eeee), eee M(M-8-Mee)8 (8.88 e, 8 eeee) eeee eeeeee ee e eeeee eeee eee eeee eeeeeeeeeeee eeeeee eeee M8. Mee-8-eee (88 eM, 8.8 eee) eee MeMM (88 eM) eeee eeee eeeee, eee eee eeeeeee eee eeeeee eeee eeeeeeee ee 88°M. MMM eee eeee eeeeeeeeeeee eee eeee eee eeeeeee ee eeeeeee e eeeeee ee eee M8 eeeeeee e eeee eeeeeeeeee eee MMM ee 8°M. Mee eeeeeeee eee eeeeeeeee eee 8.8 e, eeeeee eeeee eeee MMM (8.8 eM, 88 eeee) eee eeeee ee eee eeeeee. MMM eeeeeeee eeeeeeeee eeee e eeeeeee eeeeeeeeee ee eeeeeeeeeeeeee eee 8-eeeeeeeeeeeeeeeeeee (88:88) eee eeeeee; eeeee: 8.8 e [888% (eeeee ee MMM eeeeeeee)].

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

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References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8e, 888.
• 8.Meeeee-Meee, (8888) M 8-8, 8888.
• 8.Meeeee-Meee, (8888) M 88-8, 888.
• 8.Meeeee-Meee, (8888) 88/8e, 888.
• 8.Meeeee-Meee, (8888) M 88-8, 888.
• 8.Meeeee-Meee, (8888) M 88e, 8888.
• 8.Meeeee-Meee, (8888) M 88e, 8888.