Science of Synthesis

Marsden, S. P., Science of Synthesis, (2005) 26, 1060.

The uncatalyzed addition of nucleophiles to alkenyl acid halides is complicated by the propensity for the latter species to act as Michael acceptors and this is not a generally useful approach to enones. The use of transition-metal (and particularly palladium) catalysts to promote the addition of less reactive organometallics to alkenyl acid halides is, however, a viable process. The reaction works for tetraarylborate salts using “ligandless” palladium catalysts[‌68‌] or phosphine-coordinated palladium (‌Scheme 18‌).[‌69‌] Organostannanes such as ‌73‌ can also be used as nucleophiles.[‌70‌] An interesting variant of this reaction involves the reaction of β-stannylenones such as ‌74‌ with unsaturated acid halides. The presumed intermediate dienedione suffers reduction under the reaction conditions to yield enone ‌75‌ bearing a γ-ketone function.[‌71‌] Organozincs also couple smoothly with acid halides to yield enones, with the ease of preparation and reaction of functionalized organozincs such as ‌76‌ making this a significant approach to polyfunctional enones, e.g. ‌77‌.[‌72‌]

‌Meeeee 88‌ Meeeeeeeee-Meeee-Meeeeeeee Meeeeeee ee Meeeeeeeeeeeeee eeee Meeeeeeeeee Meee Meeeeee[‌88‌–‌88‌]

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8,8-Meeeeeeeeeee-8-ee-8-eee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee MeMMe8 (8.888 e, 8 eeee), 8-eeeeeeeeee-8-eeeee eeeeeeee (8 eeee), Me(MMe8)8 (8.888 e, 8.88 eeee), eee ee eeeeeeeeeee eeeeee ee ee eeeeeeee eeeeeeee ee MMM (88 eM) eee eeeeeee ee 88°M eee 88 e. Mee eeeeeeeeeee eee eeeeeee ee eeeeeeeeee eee eee eeeeeeee eee eeeeee eeee e eee. ee MeMe (888 eM) eee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeee eeeeee eeee M8M, eeeee (MeMM8), eee eeeeeeee ee MM; eeeee: 88%.

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References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88e8, 888.