Science of Synthesis

Chartoire, A.; Nolan, S. P., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013) 1, 520.

Alkynylsilanes ‌27‌ can be coupled with propargyl chlorides ‌28‌ in the presence of a catalytic amount of copper(I) iodide and a fluoride source to yield the corresponding 1,4-skipped diynes ‌29‌ in good yields (‌Scheme 8‌).[‌34‌] The reaction can be promoted by either cesium fluoride or tetrabutylammonium fluoride and requires a polar solvent such as 1,3-dimethylimidazolidin-2-one at 80 °C. It is noteworthy that the reaction does not proceed if the substrate bears a nitrogen atom (pyridine or amine). A similar procedure has also been reported allowing the alkynylation of allyl halides in the presence of potassium fluoride and copper(I) iodide in dimethylformamide.[‌35‌]

‌Meeeee 8‌ Meeee Meeeeeee ee Meeeeeeeeeeeee eeee Meeeeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 8‌

M8	M8	Meeee (%)	Mee
(MM8)8Me	Me	88	[‌88‌]
Me	Me	88	[‌88‌]
	Me	88	[‌88‌]
	MM8M≡MMe	88	[‌88‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Mee eeeeeeeeeeeee ‌88‌ (88.8 eeee) eee eee eeeeeeeee eeeeeeee ‌88‌ (88.8 eeee) eeee eeeee ee 8,8-eeeeeeeeeeeeeeeeeeee-8-eee (88 eM) ee ee. MeM (888 ee, 8 eeee, 88 eee%) eee eeeee MeM (8.88 e, 88 eeee) eeee eeeee eeeeeeeeeeee ee ee. Meee eeeeeee eee eeeeeee ee 88 °M eee 8 e, eee eee eeeeeeee eee eeeeeeee ee MM. Meee eee eeeeeeee eee eeeeeeee, eee eeeeeee eee eeeeeee eeee Me8M (88 eM) eee 88% ee MM8MM (88 eM). Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 ×). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (88 eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee) ee eeeee eee eeee eeeee ‌88‌; eeeee: 88–88% (eeee eeeeeeee).

References