Science of Synthesis

Milata, V.; Rádl, S.; Voltrová, S., Science of Synthesis, (2008) 32, 658.

The Horner modification of the Wittig reactions (also known as the Horner–Wadsworth–Emmons, Horner–Emmons, or Wittig–Horner reaction) is usually more efficient than the classical Wittig reaction, although the synthesis of the necessary α-alkoxyphosphonates can be troublesome because the starting α-halo ethers are unstable and frequently behave as irritants.[‌184‌,‌185‌] However, in the case of α-methoxyallyl derivatives, the phosphonates ‌207‌ can be prepared from dimethyl acetals ‌206‌ in a one-pot reaction with trimethyl phosphite and phosphorus trichloride (‌Scheme 96‌).[‌186‌] The resulting α-methoxyallyl phosphonates ‌207‌ react with aldehydes or ketones to give the corresponding methoxy dienes ‌208‌ in good yields.

‌Meeeee 88‌ Meeeeeeeeee ee α-Meeeeeeeeeee Meeeeeeeeeee eee Meeee Meeeee–Meeeeeeee–Meeeee Meeeeeee Me Meee Meeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

α-Meeeeeeeeeeeeeeeee, e.e. ‌888‌, eee eeee ee eeeeeeee ee eeeeeeeee ee ee eeeeeeeeeeee eeeeeee eeeeee eeee e eeeeeeee eeeeeeeee ee eee eeeeeeee ee e Meeee eeee, eeee ee eeeee eeeeeeeeeee. Meeeeeee eeeee eeeeeeee eeee eeeeeeeee-8-eee ee eeeee eeeeeee eeeeeeeeeeeeeeee ee e eeee eeeee eee eeeeeeeeeeeee eeeee eeeeee ‌888‌ ee eeee eeeeee (‌Meeeee 88‌);[‌888‌] eeeeeeeeeeeee, eee eeeeeeee ee eee eeeeeeeeee eeeeeeee eeeeeeeeeee eeeeee eeee eee eeeeeeee eeeeeeeee-8-eee eeeee eeeeeeeeee eeee eeeeee ee eee eeeeeeeeeeeee eeeeeee. Meee ee eeeeeee eee α-eeeeeee eeeee eeeeeee eeeeeeeeeeeeeeeee eeeeeeeeee ee eee eeeeeeeee eeee ee e eeeeee ee eee α-eeeeee. Mee eeeeeeee ee eeeee eeeeeee, eee ee ee eee eeeeeee ee eeeeeeeee-8-eee; eee eeeeeee, 8M-eeeeeee-8-eee eeee eeeee e eeee eeeee ee eee eeeeeeeeeeeee eeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeeeee ee 8-[Meeeee(eeee)eeeeeeeee]eeeeeeeeeee ee eee Meeeee–Meeeeeeee–Meeeee Meeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

e Meeeeeeeee eeeee eeeeeee ‌888‌ eeee Me8 = 8-MMM8M8.

Meeeee 8-eeeeeeeeee-8-eeeeeee ‌888‌ eee eeeeeee eeeeeeee eeee eeeeeeeee ee eeeeeee ‌888‌ ee Meeeee–Meeeeeeee–Meeeee eeeeeeee eeee eeeeee (eeeeeeeeeeeeeeeeeee)eeeeeeeeeeeeee (‌888‌) (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeee 8-Meeeeeeeee-8-eeeeeee ee eee Meeeee–Meeeeeeee–Meeeee Meeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeee (8-Meeeeeeeeee-8-eeee)eeeeeeeeeee (‌888‌, M8 = M8 = M); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeeee eeeeeeeee ee eeeeeeeee eee eee e eeeeeeee, eeeeeeeee eeee. Meeeeee eeeeeeee. Meeeee eeee eee eee eeeeeeee. Meeeeeeee eee eeeeeeeeee ee eee eeeeeeeeeee eeeee.

M eeee ee (MeM)8MMMM=MM8 (8.8 eee) ee eeeeeee (88 eM) eee eeeee ee MMe8 (8.888 eee) ee eeeeeee. Mee eeeeeee eeeeee eeee, eee eeee eee eeeeeee eeeeee eee eeeeeeee (∼8 eee), M(MMe)8 (8.88 eee) eee eeeee eeeeeeee. Mee eeeeeee eee eeeeeee ee ee eee 8 e, eee eeee eeeeeeeeeeee eeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeeeee eeeeee; eeeee: 88%; ee 888°M/88 Meee.

8-Meeeeee-8-(8-eeeeeeeeeee-8,8-eeeeee)eeeeeee (‌888‌, M8 = M8 = M8 = M; M8 = 8-MeMM8M8); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee eeeeeeeeeee ‌888‌ (M8 = M8 = M; 88 eeee) ee eeeee MMM (88 eM) eee eeeee eeeeee ee e eeee ee MMM (8.8 eeeee) ee MMM ee −88°M, eee eee eeeeeee eee eeeeeee ee −88°M eee 8 e. M eeee ee 8-MeMM8M8MMM (8.88 eeeee) ee eeeee MMM (8 eM) eee eeeee, eee eee eeeeeee eee eeeeeee ee −88°M eee e eeeeeee 8 e eeeeee eeeee eeeeeee ee eeee ee ee. Mee. ee MM8Me (88 eM) eee eeee eeeee, eee eeeeee eeee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeeee eeeeeeeee eeee Me8M. Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eee. ee MeMMM8 eee eee. ee MeMe, eeee eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeeee, eeeeeeeee eeeee/Me8M 8:8) ee eeee e eeee eeeeee eee; eeeee: 88% (8:8 eeeeeee ee M,M- eee M,M-eeeeeee).

Meeeeeee [Meeeeee(eeeeee)eeeeee]eeeeeeeeeee (‌888‌, M8 = Me; Me8 = Me); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeeee eeeeeeeee ee eeeeeeeee eee eee e eeeeeeee, eeeeeeeee eeee. Meeeeee eeeeeeee. Meeeee eeee eee eee eeeeeeee. Meeeeeeee eee eeeeeeeeee ee eee eeeeeeeeeee eeeee.

M eeeeeee ee MeM(MMe)8 (88 e, 8.88 eee), M(MMe)8 (88.8 eM, 8.88 eee; eeeeeeeeeee), eee MMMMe (88.8 e, 8.88 eee) eee eeeeeee eeeee M8 eee 88 e. Mee eeeeeeeee eeeeee eee eee eeeeee eeeeeeeee eeee ee MeMMM8, eee eeeeeee eee eeeeeeeee eeee MM8Me8, eee eee eeeeeeee eeee eeeeee eeee M8M, eeeee, eee eeeeee ee. Mee eeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeee; eeeee: 88.8 e (88%); ee 888°M/8 Meee.

8-[Meeeeee(eeeeee)eeeeeeeee]eeeeeeeeee (‌888‌, M8 = Me; Me8 = Me); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee MMM eee eeeeeeee eeee eMe8MM (8.8 eM, 88 eeee) eee e 8.8 M eeee ee MeMe ee eeeeee (88 eM, 88 eeee) ee MMM (88 eM) ee −88°M eee 88 eee. Me eeee eee eeeee eeeeeeee e eeee ee eeeeeeeeeee ‌888‌ (M8 = Me; Me8 = Me; 88 eeee) ee MMM (88 eM) ee −88°M eeeee M8. Mee eeeeeee eee eeeeeee eee 8 e, eeee e eeee ee eeeeeeeee-8-eee (8.88 e, 88 eeee) ee MMM (88 eM) eee eeeeee eeeee eeee 88 eee, eee eee eeee eee eeeeeee ee eeee ee ee ee eee 8 e. Mee eeeeeeee eee eeeeeeee ee eeeeeee eee eeeeeee eeee 8.8 M eeeeeeeee eeeeee (eM 8.8), eee eee eeeeeeeee eeeeeee eee eeeeeee eeeeeeeee eeee MM8Me8 (888 eM). Mee eeeeeeee eeee eeeeee eeee ee MeMMM8 (888 eM) eee eeeee (8 × 888 eM), eeee eeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 88:8); eeeee: 88%; ee 88–88°M (eeeeeeeee eeeee).

References

Meeeeee Meeeeeeeeee

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