Science of Synthesis

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V., Science of Synthesis, (2010) 47, 851.

An alternative one-pot procedure for the synthesis of alkenes from vic-diols is known as the Eastwood deoxygenation,[‌328‌] which like the Corey–Winter reaction depends upon the fragmentation of a 1,3-dioxolane intermediate. According to this protocol, a diol is treated with a trialkyl orthoformate at high temperature (140–180°C), followed by thermolysis of the resulting 2-alkoxy-1,3-dioxolane ‌151‌ (160–220°C) in the presence of a carboxylic acid (typically acetic acid). A related procedure is the conversion of vic-diols with (dimethylamino)dimethoxymethane into 2-(dimethylamino)-1,3-dioxolanes, which are then either quaternized in situ with iodomethane or heated under reflux in acetic anhydride, which in both cases leads to fragmentation to afford an alkene (see also Houben–Weyl, Vol. 5/1b, p 748) (‌Scheme 55‌).[‌203‌,‌244‌,‌245‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeee eeee eee-Meeee eee 8-Meeeee- eee 8-(Meeeeeeeeeeee)-8,8-eeeeeeeeee[‌888‌,‌888‌,‌888‌]

Mee eeeeeeeeee ee eeee eeeeeeeee eee eeeeeeeeeee.[‌888‌] Meee eee Meeee–Meeeee eeeeeeeeee, eee Meeeeeee eeeeee eee eeeeeeeee eeeeeeeeeeeeee ee 8-(eeeeeeeeeeeee)-8,8-eeeeeeeeee eee eee eeeeeeeeeeeeee. Meeeeeee eee eeeeeeeeeeee 8,8-eeeeeeeeee eee ee eeeeeeee ee eeee eeeeeeeeee (ee eeeeeeee ee eeeeeee), eeee ee eeeeeee eeeeeeeeeee. Meeeeeeeeee ee (8,8-eeeeeeee-8-ee)eeeeeeeeeeeeeeeee eeeeeee eeeeeeee ee eeeee eeeeeeeeeeee eeee eeee ee eeee eeeeee ee 8-eeeeee-8,8-eeeeeeeeee eee eee eeeee eeeeeeeeee eee eeee-eeeeeeeee eeeeeeeee, eee e eeeee eeeeeeee eee eeee eeeeeeeee eeeeee ee eeeeee eee.[‌888‌,‌888‌] Mee eeeeeeeeeeeeee eeeeeeee (eeeeeeeee eee eeeeeeeee ee ‌888‌ eee ‌888‌ eeee ‌888‌ eee ‌888‌, eeeeeeeeeeee) eee eeee eeeeeeee eeeeeeeeeeeee, eee ‌Meeee 88‌.[‌888‌–‌888‌]

‌Meeee 88‌ Meeeeee eeee 8-Meeeee- eee 8-(Meeeeeeeeeeee)-8,8-eeeeeeeeee[‌888‌–‌888‌]

Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeee	Meeee (%)	Mee
	Me8MMM(MMe)8, MeM, MM8Me8, ee, eeee Me8M, eeee		88	[‌888‌]
	MM(MMe)8, MMMM, MMM, 8 e, eeee Me8M, 888°M, eeeeee eeee, 8.8 e		88e	[‌888‌]
	MM(MMe)8, MMMM, MMM, eeee Me8M, 888°M, eeeeee eeee, 8 e		88e	[‌888‌]
	MM(MMe)8, MMMM, MMM, eeee Me8M, 888°M, eeeeee eeee, 8.8 e		88e	[‌888‌]
	MM(MMe)8, MMMM, MMM, 8 e, eeee Me8M, eeee, 8 e		88	[‌888‌]
	Me8MMM(MMM8e-Me)8, eeeeeee, eeee, 88 e, eeee Me8M, eeee, 88 e		88	[‌888‌]
	MM(MMe)8, MeMM, 888°M, 8 e, eeee 888°M, 8 e		88	[‌888‌]

e MM eeeee.

Meeeeeeeeeee Meeeeeeee

(M)-Δ8-Meeeeeeeeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

Meeeeeeee eeee (‌888‌; 8.88 e, 88 eeee) eee eeeeeeeeeeeeeeeee eeeeeeeeeee eeeeee (8.88 e, 88 eeee) ee eeeeeee (888 eM) eeee eeeeee eeeee eeeeee eeeee e M8 eeeeeeeeee eee 88 e. Mee eeeeeee eee eeeeeeeee eee eeeee eeeeeee eeeeeeee, Me8M (888 eM) eee eeeee, eee eee eeeeeee eee eeeeee eeeee eeeeee eee eeeeeee 88 e. Me eee eeee eeeeeeee, eee Me8M eee eeeeeee ee eeeeeeeeeeee. Mee eeeeeeeee eee eee eeeeeeeee ee e Meeeeeeee eeeeeeeee ee 888–888°M/8.8 Meee ee eeee eee eeeeeee ee e eeeeeeeee eeeeee (8.8 e), eeeee eeee eeeeeeee (8.8 e). Meeeeee eeeeeeeeeeeeeeee ee eee eeeeeee ee eeeeeeeeeeee eeee eeeee MeMe8 eeee ee eeeeeeeeee eeeeee ee eeeeeee; eeeee eeeee: 8.88 e (88%); MM (eeee) ν̃eee: 8888, 8888, 888 ee-8; 8M MMM (MMe8, δ): 8.8 (e, 88M), 8.8–8.8 (e, 8M), 8.8 (e, 8M), 8.8 (e, 8M).

(M)-8,8-Me-8-eeeeeeeeeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee eeee-8,8-ee-8-eeeeeeeeeeeeeee-8,8-eeee (‌888‌; 888 ee, 8.88 eeee), MM(MMe)8 (8 eM, 88 eeee), eee MeMM (8 ee, 8.88 eeee) eee eeeeee ee 888°M eee 8 e, eee eeee eeeeeee ee eeee ee ee. Mee eeeeeee eee eeeeeee eeee 88% ee Me8MM8 (88 eM) eee eeee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeeeeeeeeeee eeee M8M (88 eM) eee eeeee (88 eM), eee eeee eeeee (MeMM8). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeee 8-eeeeee-8,8-eeeeeeeee (eeeeeee ee eeeeeee; 888 ee, 88%). Meee eeeee eeeeeeee eee eeeeee ee 888°M eeeee ee eeeee eeeeeeeeee eee 8 e, eeeeee ee ee, eee eeeeeeee eeee 88% ee Me8MM8 (88 eM), eee eee eeeeeeeee eeeeeeeeee eee eeee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeeeeeeeeeee eeee M8M (8 × 88 eM) eee eeeee (88 eM), eee eeee eeeee (MeMM8). Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee) ee eeee e eeeeeeeee eeeeeeeeeeeeeeee eeeee; eeeee: 888 ee (88%; 88% eeee eeee); ee 888–888°M; MM (MMe) ν̃eee: 8888, 8888, 8888, 8888, 8888, 8888 ee-8; 8M MMM (MMMe8, δ): 8.88–8.88 (e, 88M), 8.88–8.88 (e, 88M), 8.88 (ee e, 8M), 8.88 (e, 8M); 88M MMM (MMMe8, δ): 88.88 (e), 88.88 (e), 88.88 (e), 88.88 (e), 888.8 (e).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8e, 888.