Science of Synthesis

Lipton, M. F.; Mauragis, M. A., Science of Synthesis, (2005) 21, 543.

Elimination reactions of suitably substituted α-, β-, α,β-, β,γ-, and γ,δ-amides are capable of yielding unsaturated and polyunsaturated amides. Samarium(II) iodide can be employed to generate E-α,β-unsaturated amides by β-elimination of readily available 2-chloro-3-hydroxy amides. For example, by treating 2-chloro-3-hydroxy amide ‌27‌ with samarium(II) iodide in tetrahydrofuran at room temperature, the amides ‌28‌ are obtained after a few minutes (‌Scheme 11‌).[‌29‌] Only preliminary results are presented, but isolated yields between 82–90% are obtained with E selectivities over 98%.

‌Meeeee 88‌ Meeeeeee ee Meeeeeee(MM) Meeeee eeee 8-Meeeee-8-eeeeeee Meeeee[‌88‌]

Me e eeeeeee eeeeeee ee eee M-eeeeeeeee ee eeeeeee-8,88-eeeeee,[‌88‌] e eeee eeeeeeeee/eeeeeeeeeee eeeeeeeee eee eeeeeeeee eee eee eeeeeeeee ee 8-eeeeeeeeeeeeeeee-8-eeee. Meeeeeeee ee eee eeeeeeee eeeeeeeeeeee-8-eee ‌88‌ eeee 8-eeeeeeeeeeeeee eeeeeeeee ‌88‌ eeeeeeee ee ee eeee eeeeeeeeeee eeeee eeeeeeeee eeeeeeeee eeeeeee eee α,β-eeeeeeeeeee eeeeee ‌88‌ ee 88–88% eeeeee eee eeee ee'e eeee 88.8% (‌Meeeee 88‌).[‌88‌] Mee eeeeee ee eeeeeeeeee ee 8-eeeee eee 8-eeee eeeeeeeeeee 8-eeeeeeeeeeeeee eeeeeeeee, eeeeeeeee eee eeeeeeee eeee M eeeeeeee. Meee eeeeee ee eeee eeeee ee ee eeeeeeeee eeee Meeeeeee'e eeeeeee-8,88-eeeeee eeeeeeeee ee eeeeeee ‌88‌ ee eeeeeeeeee eeeeee, eee eee Meeee eeeeeeeeee-8-eee ee eeeeeeeeee.

‌Meeeee 88‌ Meeeeeeee eee Meeeeeeeeee ee 8-Meeeeeeeeeeeee Meeeeeeee[‌88‌]

Mee eeeeeeeeeee ee 8M,8M-eeeeeeeeee eee eee eeeeee eeeeeeeeeee ee β-eeeeeee eeeeeeee ee eeeeeeee, eee eeee eeeee eeeeeeeeeeee eeeeeee eee eeeeeeee.[‌88‌,‌88‌] Mee eeeeee eee 88–88% eee eee eeeeeeee eeeeeeeee eee eeeeeeeeeeee ee eee eeeeeee eeeeeee eeeeeeeeeeeee ee e eeeee eeeeeeee. Meeee eeee eeeeeeeeeee, eeeeeeee ‌88‌ eee ee eeeeeeeee eeee β-eeeeeee eeeeeeee ‌88‌ eeeee eeeeeeeee eeee eeeeeeeeeeee eeeeeeee ee eeeeeeeee ‌88‌. Meeeeeeeee eeeeee eeeeeeeeeee ee eee eeeeeeee ee eeeeeeeee eeee-eeeeeeee eeeeeeee eee 8M,8M-eeeeeeeeee ‌88‌ (‌Meeeee 88‌).

‌Meeeee 88‌ 8M,8M-Meeeeeeeee eee eee Meeeee Meeeeeeeeee ee β-Meeeeee Meeeeeee[‌88‌,‌88‌]

Mee eeeeeeeee ee γ-eeeeeee-α,β-eeeeeeeeeee eeeeee eeee eeee eeeeeeeeeeee eeeeee eee ee eeeeeeeeee eeeeeeeeeeeeeee eee eeeeeeeeeee eeeeeee eee eeee eeeeeeee.[‌88‌] Meee, eeeeeeeee ee β,γ-eeeeeeeeeee eeeee ‌88‌, eeee Meeeeeee-MM-eee-α eee eeeeeeeeeeeeeeeeee ee eeee-eeeee eeeeeee eee eeeee eeeeeee ee 88% eeeee ee eeee ‌88‌ eeee 88% ee. Meeeeeeeee eeeeeeeee eeee eeeeeee eeeeeeee eee eeeeeeeeeeeee ee eeeeeeeeeeeeeee, eeeeeeee ee 8,8-eeeeeeeeeeee[8.8.8]eeeee-8-eee, eeeeeeee eeeeeeeee eeeee ‌88‌ ee 88% eeeee (‌Meeeee 88‌). Meeeeeeeeeeee, ee eeeeeeeeeeee eeeeeee eeee eeeeeeee.

‌Meeeee 88‌ Meeeeeeee ee e γ-Meeeeee-α,β-Meeeeeeeeee Meeee[‌88‌]

Meeeeee eeeeee eeeeeeee eeeeeeee eeeeeeee eeeee eeeeeeee eeeeeeeee, eeeee eee eeeeeee e eeeeeeeeeeeeeeeeeee eee eeeeeeeee eeeeeeee ee eeee eeeeeee eeeeeeee. Meeeeee eeeeeeee ee eeeeeee eeeee eee β-eeeeeeee eeeeeeee eee eeee-eeeeeee eeeeeeeeeee ee eeeeeeeeeeeeeee eeee ee eeeeeeeeeeee, eeeeeeeee e 8:8 eeeeeee ee 8M,8M- eee 8M,8M-eeeeeee. Meeeeee eeeeeeeeeeeee ee eee eeeeeeeeeee eee eeeeeeee eeee eee eeeeeeee eee eeeeeeeee eeee eee eeeeeeeeee eeee eeeeeeeee eeeeee ‌88‌ eee eeeeeeeeee, eeeeeeeeee ee eee eeee eeeeeeeee, eee eeeeeeeee (‌Meeeee 88‌).[‌88‌] Mee α,β-eeeeeeeeeee eeeeee ‌88‌ eee eeeeeeee eeee 8M,8M eeeeeeeeeeeee ee eeee 88% eee ee 88–88% eeeeeee eeeeee eeee eee eeeeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeeeee ee Meeeeeeeeeeeeee Meee eeee β-Meeeeeee Meeeee[‌88‌]

Meeeeeeeeee ee eeeee eeeeeeeee eeeeeeee e eeeeeee eeeee ee eeeeeeee. Mee eeeeeee, eee eeeeeeee ee eeeee eeeeeeeee eeeeeeeee ‌88‌ eeee eeeeeee eeeeeeeeeeeeeeeeeeeeee eeeeeeee eee eeeeeeee ‌88‌ ee eeeeeeee ee eeee eeeeee (‌Meeeee 88‌).[‌88‌] Mee eeeee eeeeeeeee eeeeeeeee eee eeeeeee eeeeeeeee eee Meeeee–Meeeee eeeeeeee ee eee eeee-eeeee eeeeeeeeeeeeeeeeeeeeee eeee eee eeeeeeeeeee eeeeeeee eeeeeeee ee eeeeeeeeee ee eee eeeee eeeeeeeeeee ee eee 8-eeeeeee eeeeeeeee, eee eeeeeeee eeee ee eeeee.

‌Meeeee 88‌ Meeeeeeeeee Meeeeeeee ee Meeee Meeeeeeee Meeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeeeeee-8-eeee ‌88‌; Meeeeee Meeeeeeee:[88

Me e eeeeeeeeee ee eeeeeeeeeeee-8-eee ‌88‌ (8.8 e, 88 eeee) ee MeMM (88 eM) eee eeeee eee eeee eeeeeeee ‌88‌ (88.8 eeee) ee eee eeeeeee ee 88°M. Mee eeeeeee eee eeeeee ee 88°M eee 8–8 e eeeee M8 eee eeeeee ee ee. M8MM8 (8.8 e, 88.8 eeee) eee eeeee eeeeeeeeeee eeee 88 eee eee eee eeeeeee eee eeeeee ee 88°M eee 8–8 e, eee eeeeee ee ee. Mee eeeeeeeee eeeeeeee eeee eeeeeee eee eeeeeeeeee eee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eeeeeee eee eeeeeeeeeee eeeeeee MM8Me8 eee M8M, eee eee eeeeeee eeeee eee eeeeee eeee eee. Me8MM8 eee eee. MeMe, eeeee (MeMM8), eee eeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeeeeee (MeMM/M8M 8:8, 8 eM·e−8 eeeeeeeee) ee 8°M ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88); eeeee: 88–88%.

8M,8M-Meeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Meeeeee ‌88‌ eee eeeeeee eeee MeMe (8.8 eeeee) ee MMM ee –88°M eee 8 e. Meeeeeee ‌88‌ eee eeeee eeeeeeee ee –88°M ee eeee eeee, eee eee eeeeeeee eee eeeeeeeee ee eeee eeeeeeeeeee eee 8.8 e. Mee eeeee β-eeeeeee eeeeeee eeee eeeeeeee eee eeeeeee eeee Me8M eee eeeeeeee ee eeeeeee eee eeeeeeeeeeeee β-eeeeeee eeeeeee ‌88‌ eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee). M eeee ee eee eeeeeee ‌88‌ (8.8 eeee) ee e-MeMM (88 eM) eee eeeeeee eeee e-MeMM (8.8 eeee) ee ee eee 88 e. Meeeeeeee ee eee eeee eeeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeeee eeeeeee); eeeee: 88–88%.

(8M,8M)-M-Meeeeeeeeeeeee-8,8-eeeeeeeee [‌88‌, M8 = (MM8)8Me]; Meeeeee Meeeeeeee:[‌88‌]

e-MeMM (88 ee, 8.88 eeee) eee eeeee ee e eeeeeee eeee ee eeeee ‌88‌ [M8 = (MM8)8Me; 888 ee, 8.88 eeee] ee MMM (8 eM) ee 88°M. M eeeeeeeeeee eeeeee eeeeeeeeeee, eee eeeeeeee eee eeeeeeeee eee 88 eee. M8M (8 eM) eee eeeee eee eee eeeeeee eee eeeeeeeee eeee eeeeeee eeeeeeee ee Me8M. Mee eeeeeee eeeee eee eeeeee eeee M8M eee eeeee, eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeeeee ee eeeeee-eeeee eeeeeeee; eeeee: 88 ee (88%).

8-(Meeee-8-ee)eeee-8-eeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Mee eeeee eeeeeeee ‌88‌ (8.88 eeee) ee MMM (88.8 eM) eee eeeeee ee –88°M eee MeMMMM (8 eeee) eee eeeee eeeeeeee. Mee eeeeeee eee eeeeeee ee eeee eeeeeeeeeee eee 8 e eeee eeeeee ee 88°M eeee 8 e. M eee. eeee ee MM8Me (88 eM) eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee, eeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee); eeeee: 88–88%.

References

Meeeeee Meeeeeeeeee

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