Science of Synthesis

Tracey, M. R.; Hsung, R. P.; Antoline, J.; Kurtz, K. C. M.; Shen, L.; Slafer, B. W.; Zhang, Y., Science of Synthesis, (2005) 21, 416.

The synthesis of enamides can be achieved via a copper(I)-catalyzed coupling of vinyl iodides and amides. In some cases the products are the starting materials for macrolides.[‌74‌] An example of this type of coupling reaction is shown in ‌Scheme 44‌ where (2E,4E)-N-[(1E)-hept-1-en-1-yl]hexa-2,4-dienamide (‌86‌), can be obtained from the amide ‌84‌ and the iodide ‌85‌ using copper(I) thiophene carboxylate (CuTC) as the coupling agent. This methodology is used in the syntheses of antitumor natural products bearing an enamide side chain, such as the lobatamides A–F,[‌75‌,‌76‌] oximidines I–III,[‌77‌,‌78‌] and CJ-12,950.[‌79‌]

‌Meeeee 88‌ Meeeeeeee ee ee Meeeeee ee Meeeee(M)-Meeeeeeee Meeeeeee ee ee Meeee eee e Meeee Meeeee eeee Meeeee(M) Meeeeeeeeeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M,8M)-M-[(8M)-Meee-8-ee-8-ee]eeee-8,8-eeeeeeeee (‌88‌):[‌88‌]

(8M,8M)-Meee-8,8-eeeeeeeee (‌88‌; 88 ee, 8.88 eeee), eeeeee(M) eeeeeeeeeeeeeeeeeeee (MeMM; 88.8 ee, 8.88 eeee), eee Me8MM8 (888 ee, 8.88 eeee) eeee eeeeee ee ee eeee-eeeee Meeeeee eeeee (88 eM) eeeeeeee eeee e eeeeeee eee. Meeee MMM (8 eM) eee eeeee eee e eeeeeee. Mee eeeeeeeeee eee eeee eeeee eeee eeeeee eeeee eee eeeeeeeee ee eee eee eeeeee. (M)-8-Meeeeeeeeee (‌88‌; 888 ee, 8.8 eeee, 88 μM) eee eeeee eeeee e eeeeeeeeee eeeeeee. Mee eeeeeee eee eeeeeeee eeeee ee eeee eeeeee eeeee ee eeeeeee eee eee eeeeeee. Mee eeeeeeeeee eee eeeeeee ee 88°M eee 88 e eeeee eeeee. Mee eee eeeeee eee eeeeee ee ee, eee eeeeee eeee Me8M. Mee Me8M eeeeee eeee eeeeeeee eee eeeeee eeee e eM 8 eeeeee. Mee eeeeeee eeeee eee eeeeeeeee eeeee eeee eeee Me8M eee eee eee eeeeeee eeeeee eee eeeeeeee eeee eeeeeeee, eeeee (Me8MM8), eee eeeeeeeeeeee ee eeee e eeeeeeeee eeeee, eeeee eee eeeeeeeeeeeeeee (eeeeee eee, 8% Me8M/MeMMe/eeeeee); eeeee: 88 ee (88%).

References