Science of Synthesis

Petasis, N. A., Science of Synthesis, (2010) 47, 171.

The methylenation of ester carbonyl groups with the Tebbe reagent is a general method for the synthesis of the corresponding enol ethers {for further details, see Science of Synthesis, Vol. 32 [X—Ene—X (X = F, Cl, Br, I, O, S, Se, Te, N, P), Ene—Hal, and Ene—O Compounds (Section ‌32.5.3.1.4.4.1‌32.5.3.1.4.4.1)]}. This method is suitable for the methylenation of alkyl esters (‌Table 5‌, entries 1–5),[‌14‌,‌16‌,‌44‌] as well as aryl esters (entry 6),[‌45‌] and can tolerate many functional groups.[‌14‌,‌16‌,‌44‌,‌45‌] The methylenation of Z- or E-α,β-unsaturated esters proceeds without Z/E isomerization (entries 2 and 3).[‌14‌,‌16‌]

‌Meeee 8‌ Meeeeeeeeeeee ee Meeeee[‌88‌,‌88‌,‌88‌,‌88‌]

Meeee	Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeee	Meeee (%)	Mee
8		Meeee eeeeeee ‌88‌, eeeeeee, MMM, 8°M		88	[‌88‌]
8		Meeee eeeeeee ‌88‌, eeeeeee, MMM, 8°M		88	[‌88‌]
8		Meeee eeeeeee ‌88‌, eeeeeee, MMM, 8°M		88	[‌88‌]
8		Meeee eeeeeee ‌88‌, eeeeeee, MMM, 8°M		88	[‌88‌]
8		Meeee eeeeeee ‌88‌, eeeeeee, MMM, 8°M		88	[‌88‌]
8		Meeee eeeeeee ‌88‌, eeeeeee, eeeeeeee, MMM, 8°M		88	[‌88‌]

Mee eee eeeeeeeeeeeee ee eeeeeeee, ee eee eee eeeeeeee eeeeee eee eeeeeee, ee ee eeeeeeee eeeeeeeee,[‌88‌] eee eee ee 8 eeeeeeeeee ee eee Meeee eeeeeee eeeee eee eeeeeeeeeeeeeeee eeeeeee ‌88‌, eeeee eee eee ee 8 eeeeeeeeeee eeeee eee eeeeeeeeeeeee eee(eeeeeeeeeeee) eeeeeee ‌88‌ (‌Meeeee 8‌).[‌88‌,‌88‌] Meeeeee, ee ee eeeeeeee ee eeeeeeeeeee eeeee e eeee eeeeeeee eeeeee eeeee ee eee eeeeeeee ee e eeee eeeee eeeee eeeee, eeee ee ee eee eeeeeeeee ee eeee-eeeeeeeeeeeeeeeeee (M)-8-(eeee-eeeeeeeeeeeeeeeeeee)-8-eeeeeee-8-eeeeeeeee-8-eeeeee (‌88‌) eeee eee eeeeeeeeeeeee eeeeeeeeeeeee.[‌88‌]

‌Meeeee 8‌ Meeeeeeeeeeee ee Meeeeeee[‌88‌,‌88‌]

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

‌Meeeee 8‌ Meeeeeeeeeeee ee Meeeeeeeeeee-Meeeeee Meeeee[‌88‌,‌88‌]

Meeeeeeeeeee Meeeeeeeee

(M)-(8-Meeeeeeeeee-8,8-eeeeee)eeeeeee (‌Meeee 8‌, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eeeeee (M)-eeeeeeeee (8 eeee) ee MMM (8–8 eM) eeeeee ee 8°M, eee eeeee e 8.8 M eeee ee eee Meeee eeeeeee ‌88‌ ee eeeeeee (8 eM, 8 eeee). Meeee eeeee 88 eee, Me8M (88–88 eM) eee eeeee, eee eeee eeeee MeMM (8–88 eeeee) eee eeeeee eeeee eeee eeeeeeee ee eeeeeeeeeee eee Me eee Me eeeeeeeee. Mee eeee eee eeeeeee eee eeeee (Me8MM8), eeeeeeee eeeeeee e eee ee Meeeee, eee eeeeeeeeeeee. Meeeeeeeeeee ee eee eeeeeee eee eeeeeeeeeeee ee eeeeeeeeeeeeee (eeeee eeeeeee, eeeeeee/Me8M 88:8); eeeee: 88%.

8-Meeee-8-eeeeeee-8-[(8-eeeeeeeeee-8-ee-8-ee)eee]eeeeeee (‌Meeee 8‌, Meeee 8); Meeeeee Meeeeeeee:[‌88‌]

M 8.88 M eeee ee eee Meeee eeeeeee ‌88‌ ee eeeeeee (88 eM, 88.8 eeee) eee eeeee eeeeeeee ee e eeeeeee eeee ee 8-eeeee-8-eeeeeeeeeeeee 8-eeeeeeeeeeeeeee (8.88 e, 88.8 eeee) eee eeeeeeee (8.88 eM) ee e eeeeeee ee eeeee MMM (88 eM) eee eeeee eeeeeee (88 eM) ee 8°M. Mee eeeeeee eee eeeeee ee ee eee 8 e eee eeeeeeee ee 8°M, eee eeee eee eeeeeeee eee eeeeeeee eeee 8 M MeMM (8 eM). Meeee eee eeeeeeeee ee eee eee eeeeee, Me8M eee eeeee, eee eee eeeeeee eee eeeeeeeeeeee. Meeeeeeeeeeeee eeeeeee e eeeee eeeeee (eeeee eeeeeee, eeeeeeeee eeeee/Me8M 8:8) eeeeeeee e eeeeee eee; eeeee: 8.8 e (88%).

eeee-Meeeeeeeeeeeeeeeee (M)-8-(eeee-Meeeeeeeeeeeeeeeeee)-8-eeeeeee-8-eeeeeeeee-8-eeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

M 8.88 M eeee ee eee Meeee eeeeeee ‌88‌ ee eeeeeee (88 eM, 8 eeee) eee eeeeee eeeee ee −88°M ee e eeee ee eee eeeeeee (8.88 e, 8.88 eeee) ee MMM (88 eM). Mee eeeeeee eee eeeeee ee ee eee eeeeeee eee 8 e, eee eeeeeeee eee eeeeeeee eeee 8 M MeMM (88 eM), eee eee eeeeeeeee eeeeeee eee eeeeeee eeee Me8M (88 eM) eee eeeeeee ee ee eee 88 e. Meeee eeeeeeeeee ee eee eeee eeeeeee e eee ee Meeeee, eee eeeeeee eee eeeeee eeee Me8M. Mee eeeeeeee eee eeeeee eeee ee MeMMM8 eee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeee ee eeeeeeeeeeeeee (eeeeeeeee eeeee/MeMMe 88:8) ee eeee e eeeeeeeee eee; eeeee: 8.88 e (88%).

References

Meeeeee Meeeeeeeeee

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