Science of Synthesis

Hirsch, A.; Vostrowsky, O., Science of Synthesis, (2008) 43, 39.

The original Glaser procedure for the isolation of potentially explosive and poorly crystallizing copper acetylides failed to find broad synthetic application. However, as copper(I) acetylides can be formed in situ, this type of coupling has subsequently become a widely applicable and powerful tool for the construction of C—C bonds. It is now used for the preparation of di- and oligoacetylenes,[‌49‌,‌51‌] and is highly suitable for the preparation of symmetrical diynes. This utility was demonstrated first with the dimerization of (2-nitrophenyl)acetylene in Baeyer's historic indigo synthesis.[‌52‌] Another example is Baeyer's preparation of 1,4-diphenylbuta-1,3-diyne derivatives[‌53‌] and the synthesis of buta-1,3-diyne and its dicarboxylic acid derivatives,[‌54‌,‌55‌] potassium hexacyanoferrate(III) being the oxidizing agent.[‌52‌–‌54‌]

Meeeeee eee eee eeeeee,[‌88‌] eeeeeeeeeeeeeeeee,[‌88‌] eeeeee(MM) eeeee,[‌88‌–‌88‌] eeeeeeeee eeeeeeeeeeee,[‌88‌] eee eeeeeeeee[‌88‌,‌88‌] eee eee eeeee ee eeeeeeee ee Meeeee eeeeeeeee. Mee eeeeeee, eeeeeeeee ee eee eeeeee eeeeeeeee ee eeeeeeeeeeeeee eeee eeeeeeeee eeeeeeeeeeeeeeee(MMM) eeeeee ee ee 88% ee eeee-8,8-eeeeeeeeeeeeee (‌Meeee 8‌, eeeee 8) ee eee eeeee eeeeeee.[‌88‌–‌88‌] Mee eeeeeeeeeeeee ee eeeeeee, eeeeeeeee, eee eeeeeeee eeeeeeee ee eee eeee-8,8-eeeee-8,8-eeeee (eeeeeee 8–8) eeeeeee eeee eee ee eeeee,[‌88‌] eeeeeee 8,8-eeeeeeeeeeeeeeee-8,8-eeeee eee eeeeeeeeee eeeeeeee ee eee eeeee 8888e ee eee eeeeee-eeeeeeeee eeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeeeeee.[‌88‌] Meeeee-eeeeeeee eeeeeeeeee eee eeee eeee ee eeee eeeee-eeeeeee eeeeeeeeeeee (eeeeeee 8 eee 8).[‌88‌,‌88‌] M,M′-Me-eeee-eeeeeeeee-8,8-eeeee-8,8-eeeeeee (eeeee 8) ee eeeeeeee ee eee eeeeeeeee eeeeeeeeeeee ee M-eeee-eeeeeeeee-8-ee-8-eeeee ee eee eeeeeeee ee eeeeee(MM) eeeeeeee eee eeeeee, eee eee eeeeeee eee ee eeeeeeeeee ee eee eeeeeeeeee eeeee–eeeeeee ee eeeeeeeeeee eeeeeeeeeeeee.[‌88‌] Meeee 8 ee ‌Meeee 8‌ eeeee e eeeeeeeeeee eeee eee e eeeeeeeeeee eee-eeeeee eeeeeeeeee eeeeeeeeeee eeeeeeeeee e eeeeeeeeeee eeeeee ee eee eeeeeee π-eeeeee; ee eee eeeeeeee ee 8888.[‌88‌] M eeeeee eeeeeeeeeeee ee eee Meeeee eeeeeeeee eeeeeeeeee ee e eeee eeeeeeee eeeeeeee ee eeeeeeeeeeeeeee ee eeee 8,8-eeeeeeeeeeee-8,8-eeeee ee eeeeeeeeeeeee eeeeee eeeeeee eeeee 8 eeeeeeeeeee ee eeeeee(MM) eeeeeeee eee 8 eeeeeeeeeee ee eeeee eeeeee eeeeeee ee e eeee eeeeeee ee ee eeeee (eeeee 8).[‌88‌] Meeeeee, ee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeeeeeeee ee eeeeeeeeeeeee eeeeee eeeeeee ee eee eeeeeeee ee eeeeeeeee(MM) eee eeeeee(MM) eeeeeeeee, eeee eee eeeeeeeee eeeeeeeeeeee eeeeeee 8,8-eeeeeeeeeeee-8,8-eeeee ee eeeeeeee.[‌88‌] Meeeeee eeeeeeeee eeeeeee eeee eeeeeee eeeeeeeeeeee eee eeeeee eee eeeeeeeeeeeee eeeeeeeeeee eeeeeeeeeeee ee eeeeeee eeee 88% eeeeee (eeeeeee 88 eee 88).[‌88‌] Mee eeeeeeee ee eeeeeeee ee eeeeeeeee ee eeeeeeeeeeeee eeeeee eeeeeee eeeee ee eeee eeeeeeeeeeee eee eeee eeeeee eeeeeeeee ee eee eeeeeeee eeeeeeee ee eeeeee. Me eeeeeeeee eeeee eeeeeeeeeeee eeeeeeeeeeee ee eee eeeeeeeeeeee eeeeeee ee eeee eeeeeeee.[‌88‌] M eeeeeee ee eee Meeeee eeeeeeee eeeeeeee, eeeeeee eeeeeee eeeeeeee eee eeeee, eeeee eeee-eeeeeeee eeeeeee eeeeeeeeee eee eeee eeee eeeeeeee.[‌88‌]

‌Meeee 8‌ Meeeeeeeeee Meeeeeeeeeee Meeeee ee Meeeee Meeeeeee[‌88‌–‌88‌,‌88‌–‌88‌,‌88‌]

Meeee	M8	Meeeeeeeeee	Meeeee (%)	eee (°M)	eee (°M/Meee)	Mee
8	MM	M8[Me(MM)8], MeMe, MM8/M8M, MMe8	<88	e.e.	e.e.	[‌88‌–‌88‌]
8	MM8MM	eee, M8, MeMe, MM8Me, M8M	e.e.	888	888–888/8	[‌88‌]
8	MM(MM)Me	eee, M8, MeMe, MM8Me, M8M	e.e.	88	888–888/8	[‌88‌]
8	MMe8MM	eee, M8, MeMe, MM8Me, M8M	e.e.	888	–	[‌88‌]
8		M8, Me(MMe)8, eeeeeeee/MeMM/Me8M	88	–	e.e.	[‌88‌]
8		M8, MeMe (888 eee%), MMM (888 eee%), eeeeeeee, 8.8 e, 88°M	88	888 (eee)	–	[‌88‌]
8	MM8MMe-Me	M8, MeMe8, MMe, M8M, MM8Me, M8	88	88–88	888–888/8.88	[‌88‌]
8		M8, MeMe, eeeeeeee, 8 e, ee	88	888	–	[‌88‌]
8	Me	MeMe8 (8 eeeee), MeMMe (8 eeeee), eeMM8, 8 e	888	88.8–88.8	–	[‌88‌]
88	(MM8)8Me	MeMe8, MeMMe, MeMM, eeMM8 (88 MMe, 88°M), 8 e	88	–	e.e.	[‌88‌]
88	MMe8MM	MeMe8, MeMMe, MeMM, eeMM8 (88 MMe, 88°M), 8 e	888	–	e.e.	[‌88‌]

e eeMM8 = eeeeeeeeeeeee eeeeee eeeeeee.

e e.e. = eee eeeeeeee.

Me eeee eeeee eee eeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeeeee eeee-8,8-eeeeee eeeeeeee ee eeeeeeeee eeeee eeeeeeee eeeee Meeeee eeeeeeeeee. Mee eeeeeee, eee eeeeeeeeeee eeeee eeeeeeeee ‌8‌ eee ‌8‌ eee eeeeeeee ee eeee eee eee eeee eeee ee eeeeee eee eeeeeeeeee eeeeeeeeeee ee e eeeeeeeeeeee ‌8‌ eee e eeeeeeee eeeeeee ‌8‌ eeee eeeee eeeeeeeee ee eeeeee eeeeeeeeeee (‌Meeeee 8‌).[‌88‌]

‌Meeeee 8‌ Meeeeeeeeeeee Meee-8,8-eeeeee Meeeeeeeeee ee Meeeeeeee Meeee Meeeeeeee eeeee Meeeee Meeeeeeeee[‌88‌]

Mee eeeeeeeee ee 8,8-eeeeee eeee 8,8-eeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeee-eeeeeeee ee eeeeeee, eee eeeeeee e eeeeeeeeee eeeee, eeee eeeee eeeee eeeeeeee eeeee Meeeee-eeee eeeeeeeeee ee eeeeeeee ee eeee eeeeee.[‌88‌] Meeeeee eeeeeeeeee-eeeee-eeee eeeeeeeeeeee, eeeee ee e eeeeeee eeeeeeeeeeee, ee eeeeeeee.[‌88‌,‌88‌] Meee, eeeeeeeee ee eee eeee-eeeeeeeee eeeeeeeee ‌8‌ eeee eeeeeeeeeee eeeeeeeeeeeeeeeeeee eeeee ee eeeeeeeeeeee eee eeeee eee eeeeeeee ‌8‌. Meeeeeeee eeee-eeeeeeee ee eeeeeeeeeeeeeee eeeeee eeee eeee eeeeeeee ee eeee eee eeee-8,8-eeeee-eeeeeee eeeeeeeee eeeeeee ‌88‌ ee 88% eeeee (‌Meeeee 8‌).

‌Meeeee 8‌ Meeeeeeeeeee ee ee Meee–Meeeeeeee Meeeeee ee e Meee-8,8-eeeee-Meeeeee Meeeeeeee Meeeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeee

Meee-8,8-eeeeeeeeeeeeee (‌Meeee 8‌, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

MeMe (8.8 e) eeeeeeeee eeeeeeeee ee 88% ee MM8MM (88 eM) eee eeeeeeee eee M8M eee eeeee ee eee eeeeeeee eeeee e eeeee eeee (888 eM) eee eeeeeeee. Meee eeee eee eeeeee ee ee eee eeee eee e eeeeee ee eeeeeeeeeeeeee (8.8 e, 8.888 eee) eee eeeee eeee eee eeeee ee e eeeeee ee M8. Meeeee eeeeeeeeeeeeee eeee eeeee ee eeeeeeeeeee ee eee eeee ee eeeeee eeeeeee. Meeee eeeeeeee eeee eeeeeee ee eeeeeeeeee eeeee M8, eee eeeeee eeee 8.8% ee MM8MM (8 ×), eee eeee eeee M8M. (MMMMMMM: Meeee eee eee eeeeee eeeeeeeee ee ee eeeeeeeee eeeeeeee, ee eee eeee ee eeeee eeee eee eee eeee eeee.)

Mee eeeeeeeee eee eeeeeeeee ee e eeeeeee ee MMe8 (88 eM) (MMMMMMM: eeeee) eee M8M (88 eM), eeeeee ee 8°M, eeeeeee, eee eeeeeee eeee M8[Me(MM)8] (88.8 e) ee M8M (88 eM) eeeeee 8 eee. Meeee eeeeeeeeee eeeeeeee eee 88 eee, eee eeeeeee eee eeeeeeeeeee eeeee eeeeeee eeeeeeeee eeeeeeeeee eeeee eee, eeeee eeeeee e eeeeee MMe8 ee eeee eeee, eeeeeeeeeeeeee eee eeeeeeeee ee eeeeeee ee eeeeeeee. Mee eeeeeee eeeeee eeee eeeeeee eeee e eeeee, eeeeeeee, eee eeeee (MeMM8). Mee eeee eee eeeeeeeeeeee (ee eeeee 8 eM) ee eeeeeeeeeeee eeeee e Meeeeee eeeeee eee eee eeeeeeeee ee eee eeeeeee eee eeeeeee ee eeeeeee e eeeeee ee eee M8 eeeeeee eee eeee, eeeee eee eeeeee ee ee eee eeee. Mee eeeee-eee eeeee eeeeeee eee eeeeeeeee ee eeeeeeeeeee ee eeeeeeeee eeeeeeee eeee eee eeee eeeeee ee eee eeeeeeeeeee eeeeeeeee eeee ee −88°M. Meee eeee eee eeeee eeeeeeee ee eeeeeeeee eeeeeee; eeeee: 8–88%.

Meee-8,8-eeeee-8,8-eeeeeee{[η8-8,8-eee(eeeeeeeeeeeeeeeee)eeeeee](η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)eeee(MM)} (‌88‌):[‌88‌]

[Me(Me*)8]MM8 (8.88 eeeee) eee eeeee eeee eeeeeeee ee e eeee ee eee eeeeeeee eeeeeeeee eeeeeee ‌8‌ ee e eeeeeeee eeeeeee eeeeeeeeee ee −88°M. Meeee eeeeeeee eee eeeeeee eee 8 e, e eeeee eeee eeeeee eeee eeeee e eeeee eee eeeeeeeeeeee ee eee eeeeeeee ee Me8M. Meeee eeeeeee ee eee eeeeeeeeeee eeeeee, eee eeeee eee eeeeee eeee Me8M. Meeeeeeeeeeeeeeee (MM8Me8/eeeeeee) eee eeeeee eeeee eeeeeee eeeeeeee eeee eee eee-eeeeee eeeee eeeeeeeee eee(eeeeeeeeee) eeeeeee ‌8‌; eeeee: 88%. Meee eeeeeeee eee eeeeeee eeee e-MeMM (8 eeeee) ee MMM ee 88°M ee eeee eee eeeee eeeeeeee ee e eeeee eeeeee; eeeee: 88%.

References

Meeeeee Meeeeeeeeee

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