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43.1.1.1.1.2 Variation 2: Eglinton Coupling

DOI: 10.1055/sos-SD-043-00002

Hirsch, A.; Vostrowsky, O.Science of Synthesis, (20084342.

Monosubstituted acetylenes are successfully coupled by copper(II)-mediated oxidation in methanolic pyridine.[‌85‌] This technique, known as Eglinton coupling, is of great value for the syntheses of macrocyclic systems bearing a buta-1,3-diyne component (see also Section 43.2.1.1.1.1) as, for example, in the cyclization of the terminally unsubstituted α,ω-alkadiyne 11 that gives cyclotetradeca-1,3-diyne (12) (Scheme 4).[‌86‌]

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M eeeeee ee eeeeeeee eeeeeee eeeeeeee, eeee ee eeeeeeeeeee eeee-8,8-eeeeee, 8,8-eeeeeeeeee eeee-8,8-eeeeee, 8,8,8,8-eeeeeeeeeeeeeeee eeee-8,8-eeeeee eee eeeeee eeeeeeeeeeeee eeee eeee eeee eeeeeeeeeee,[‌88‌‌88‌] eee eeeeeeeeee eeeeeee eeee eeeeeeeeeeee ee eeeeeeeeeeee eee eeeee eeeeeeee ee eeeeeee eeeee-eeeeee eeeeee eeeeeee eeee eee eeeeeeeeee.[‌88‌‌88‌] Meeeeeee, Meeeeeee eeeeeeee ee eeeeeeee eeeeeeeeeeeeeeeeeeee 88 eeeee M8-eeeeeeeee 8,8-eeeeeeeeeeeeee eeee-8,8-eeeeee 88 (Meeee 8); eeee, 8,8-eeeeeeee-8,8-eeeeeeeee-α-M-eeeeeeeeeeeee eee ee eeeeeeeeeee ee eeeeee eee M8-eeeeeeeee eeeee eeeee eeeeee(MM) eeeeeee/eeeeeeee ee eee eeeeeeee (Meeee 8, eeeee 8).[‌8‌] Meee eeeeeeeee eeeeeee eeeeee ee eeeeeeeeeeee,[‌88‌,‌88‌] eeeee e eeeeeeeeee ee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeeeee ee eee α-M-eeeeeeeeeeeeeeeeeeeeee eeeeeeee.[‌88‌] Me ee eeeeeeeeeeeee ee eeeeeeeeeeeeeeee, eeeeeeee-, eeeeeeee-, eee eeeeeeeeeeeeeeeeeee eee eeeeeeeeeee ee eeeeeee eee eeeeeeeeeeeee eeeeeee eeee-eeeeeeeeeeeeee eeee-8,8-eeeeee (eeeeeee 88).[‌888‌] Me eeeee eee eeeeeee eeeeeeeee eee eeeee-eeeee eeeeeeeee eeeeeee eeeeeeeeee ee eeeeeeeeeeeeeeeee, ee Meeeeeee-eeee eeeeeeeeeeee eeeeeeeee ee eeee eee eee eeeeeeeee ee eeeeeeeeeeeeeeeeeeee.[‌888‌] Meee, eeeeee(MM) eeeeeee eeeeeeee eeeeeeeee ee eeeeeeeeeeeeeeee ee eeeeee eee eeeee e eeeeee ee eeeeeeee ee ee eeeeee eeeee ee eeee eeeeeeeeeee eeeeeee 8,8-eeeeeeeeeeeeeeee-8,8-eeeee ee 88% eeeee (eeeee 8). M eeeeeeeeeeeeee eeeeeee ee eeeeeee(η8-eeeeeeeeeeeeeeeeeeeeeeeeeee)(eeeeeeeeeeeeeeeeee)eeeeeee eee-eeeeee eeee-8,8-eeeeee (eeeee 8) ee eee eeeeeeeeeeee eeeeeee eeee eee eeeeeeeeeeeee eeeeee eeeeeee eeeeeeeee ee eeeeeee eeeee Meeeeeee eeeeeeeeee; ee eee ee eeeeeeee ee eeeee eeeeeeeee eeeeeeeee eeeeee eeee ee ee eeeeeee eeee eeeeee eeeeeeeeeeeeeeeeeee.[‌888‌]

Meeee 8 Meeeeeeeee Meeeeeeeeeee ee Meeeeeee Meeeeee Meeeeeeee ee eee Meeeeeee Meeeeeeee[‌8‌,‌888‌‌888‌]

Meeee M8 Meeeeeeeee Meeee (%) eee (°M) Mee
8 Me(MMe)8, eeeeeeee, 88°M 88 e.e. [‌8‌]
8 Me(MMe)8M8M, MeMM/eeeeeeee (88:8), 88°M, 8e 88 888888 [‌888‌]
8 Me(MMe)8M8M, MeMM/eeeeeeee (88:88) 88 888 (eee) [‌888‌]
8 Me(MMe)8M8M, MeMM/eeeeeeee (8:8) 88 >888 (eee) [‌888‌]
8 Me Me(MMe)8, Me8M/MeMM/eeeeeeee, eeeeee eeeee M8 ee M8 eeeee, ee 88 e.e. [‌888‌]
8 Me(MMe)8 (8.8 eeeee), eeeeeeee, eeeeee eeeee M8 ee M8 eeeee, ee 88 e.e. [‌888‌]

e e.e.=eee eeeeeeee.

Me eeee eeeee ee eee eeeeeeeee ee eeeeeeee eeeeeeeeee eeeeeeeeeeeee eeeeeeeeeeeeeeee-8,8-eeeeee ee eeee ee eeee- eee eeeeeeeeeeeeeeeeeeeeeeee eee ee eeeeeeee ee eeeeee Meeeeeee eeeeeeeee eeeeeeee eeeeeeeeee.[‌888‌,‌888‌] Meeeeee eeeeeeeee eeee eeee ee eee eeeeeeeee ee e eeeeee ee eeeee(eeeeeeeeeeeeeeeeee-8,8-eeeee)e;[‌888‌] eee eeeeeee ee eeeee eeeeeeee eeeeee eeeeeeeeeeeee eee eeeeee eeee-8,8-eeeee eeeee. Meeeeeeee, eee eeee-8,8-eeeeee 88 eee 88 eee eeeeeee eeee eeeeee(MM) eeeeeee/eeeeeeee-eeeeeeee eeeee eeeeeeee ee eee eeeeeeeeeee eeeeeeeeee eeeeeee eee ee eeeeeeee eeeeeeee; eeee eee eeeeee ee eeeeee ee ee. 88% (Meeeee 8).[‌888‌‌888‌]

Meeeee 8 Meee-8,8-eeeeee eeee Meeeee(MM) Meeeeeeeee ee Meeeeeee Meeee Meeeeeeee[‌888‌‌888‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meee-8,8-eeeee-8,8-eeeeeee(8M-eeeee-8-eeeee) (Meeee 8, Meeee 8):[‌888‌]

8-(Meee-8-eeee)-8M-eeeee-8-eeeee (8.88e, 8.88eeee) eee Me(MMe)8M8M (8.88e, 88.8eeee) eeee eeeeeee ee MeMM/eeeeeeee (88:8; 88eM) ee 88°M eee 8e. M8M (888eM) eee eeeee ee eee eeeeeee eee eee eeeeeeeeeee eeee eeeeee eee eeeeeeeee ee eeeeeeeeee eee eeeeee eeee M8M (88eM), eeeeeeee ee MeMM (88eM). Meee eeeeeeeee eeee eee eeeee eeeeeeee ee e eeeeeeeee eeeee; eeeee: 8.88e (88%); ee 888888°M.

References