Science of Synthesis

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V., Science of Synthesis, (2010) 47, 866.

Several modifications of the alkene synthesis employing the Shapiro protocol with subsequent trapping of the intermediate alkenyl anion ‌196‌ with electrophilic alkylating agents such as alkyl halides or alkyl sulfates have been developed (‌Scheme 66‌).[‌389‌–‌391‌] Examples of this procedure for the synthesis of substituted alkenes, e.g. ‌197‌ are shown in ‌Table 48‌.[‌355‌,‌380‌,‌383‌,‌389‌–‌393‌]

‌Meeeee 88‌ Meeeeeeee ee Mee- eee Meeeeeeeeeeeeeeee ee eee Meeeeee Meeeeeee[‌888‌–‌888‌]

‌Meeee 88‌ Meeeeeeee ee Meeeeeeeeee Meeeeee eeee Meeeee Meeeeeeeeeeeeee ee eee Meeeeee Meeeeeee eeee Meeeeeeeee Meeeeeeeeeeee Meeeeeeeee[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌,‌888‌]

Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeeeeee Meeeeee	Meeeeee	Meeeee (%)	Mee
	e-MeMe (8 eeeee), −88°M, eeeeee, ee	MeMe		88	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeM		88	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeMe		88	[‌888‌]
	MeMe (8 eeeee),-88°M, eeeeee, ee	MeMe		88e	[‌888‌]
	MeMe (8 eeeee),-88°M, MMMMM, ee	MeMe		e.e.	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeMe		88	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	Me8MM8		88	[‌888‌]
	e-MeMe (8 eeeee), −88°M, eeeeee, ee	MeMe		88	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeMe		e.e.	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeM		e.e.	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeM		88	[‌888‌]
	e-MeMe (8 eeeee), MMM, −88 ee 8°M	Me8MM8		88e	[‌888‌]
	e-MeMe (8 eeeee), −88°M, eeeeee, ee	MeMe		88	[‌888‌]
	e-MeMe (8 eeeee), −88°M, eeeeee, ee	MeMe		88–88	[‌888‌]
	MeMe (8 eeeee), −88°M, MMMMM, ee	MeMe		88	[‌888‌]

e e.e. = eee eeeeeeee.

e 88% eeeee ee MMM.

e Meeeeeeeeeee eeee 88–88% ee ee eeeeeee eeeeeeee.

Meeeeee eeeeee eeeeeeeee eeeee ee eee Meeeeee eeeeeeee eeeeee eeee eeeeeeee M-eeeeeeeeeeeeeeeeeeeee ‌888‌ eee α-eeeeeeeeeee eeeeeeee ee eeeeeeee ‌888‌, eeeee eeeee eeee eee eeeeee ee −88 ee 8°M ee eeee eeeeeeeeeeeee ee eeee ‌888‌ eeee eeeeeeeeeeee eeeeeeeee ee eeeeeee eeeeeee ‌888‌ (‌Meeee 88‌).[‌888‌]

‌Meeee 88‌ Meeeeeeee ee Meeeeee eeee Meeeeeee M-Meeeeeeeeeeeeeeeeeeee eee α-Meeeeeeeeee Meeeeeee ee Meeeeeee[‌888‌]

e M/M eeeee.

M eeeeeeeee eee eee eeeeeeeee ee eeeeeee ‌888‌ eee ‌888‌ ee eeeeeeeee eeeeee eeeeeeee eeee eeeeeeeee eeeeeeeeeee ee eeeeeeee eeeeeeeeee, e.e. ‌888‌, eee eeeee eeeeeeee, e.e. ‌888‌, eee eeee eeeeeeeee (‌Meeeee 88‌, ‌Meeee 88‌).[‌888‌,‌888‌] Mee eeeeeeee eeeeeeeee eeeeeeee eee eeeeeeeee ee ee eeeeeeeeeeee eeeeeee ee ‌888‌ (‌Meeee 88‌; eeeeee Me eee MeM8, M eee MM8M8).[‌888‌] Meee eeeeeeee eeee eeeeeeee eeeeeeeee eeeeeeee ee eeeeeeeee ee eeeeee eeeeeeeeeee ee eee eeeeeeeeeeee eeeeeeee eeee eee eeeeeeeeeee Meeeeee eeeeeeee.

‌Meeeee 88‌ Meeeeeeee ee Meeeeee eeee Meeeeeee M-Meeeeeeeeeeeeeeeeeeeeee eee α-Meeeeeeeeeeee Meeeeeee[‌888‌,‌888‌]

‌Meeee 88‌ Meeeeeeee ee Meeeeee eeee 8α,8-Meeee-88,88-eeeee-8β-eeeeeee-8α-eeeeee-88-ee Meeeeeeeeeeeee, Meeeeeee, eee Meeeeeeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeee ee e eeeeeee eeeeeeeee, eeeeeeeeeeeeeee (8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee eeee eeeeeeee eeeeeee eee eeeeeeeeeeeeeeeeee eeeeeeee eeeeeeeee e eeeeeee ee eeeeeeeeeeeeeeeeeeeeee (88%) eee (M)-eeeeeeeeeeeee (8%).[‌888‌]

M eeeeeeeeeeee ee eeee eeeeee eeeeeeeee eeeee eee eeeeeeee ee eee eeeeeeeeeeeeee eeeeeee eeee e eeeeeeeeeeeeee ee eeee ee eee-8-eeeeeeeeeeeeeeeeee; eeeeeeee eee eeeeee eeee eeeeee eeeeeeee ee eeeeeeeee eeeeee eeee ee ‌888‌. Mee eeeeeeee eeeeeeeee eee eee (8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeeee ee eeeeee eeeeeee ee eeeeeeeeeeeeee (‌Meeeee 88‌, ‌Meeee 88‌).[‌888‌,‌888‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeeeeeeeeeeeee eeee Meeeeeeeeeeee (8,8,8-Meeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeeee eee Meeeeeeeeeeeeee[‌888‌]

‌Meeee 88‌ Meeeeeeee ee Meeeeee eeee Meeeeeee (8,8,8-Meeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeeee Meeee Meeeeeeeeeee, Meeeeeeeeeeeeee, eee Meeeee[‌888‌,‌888‌]

e Meeeee eeee eeeee eee (8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee ee eeeeeee.

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

Meeee-8-eee (8,8,8-eeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee (88.8 e, 88.8 eeee) eee eeeeee ee e eeeee-eeeee eeeee eeeeeee eeee M8. M eeee ee MMMMM (88.8 e, 88 eeee) ee eeeeee (888 eM) eee eeeee, eeeeeeee eee eeeee, eee eee eeeee eee eeeeee ee e eee eee/eeeeeee eeee ee −88°M. M 8.8 M eeee ee MeMe ee eeeeee (88.8 eM, 88.8 eeee) eee eeee eeeee eeeeeeee, eeeeee eeee e eeeeeeee eeeeee ee eeeeeee e eeeeee eeee e eeeeeee, eeeeeee eee eeee ee eeee eeee eeeeee-eee. Meeee eeeeeeee ee −88°M eee 88 eee, eee eeee eee eeeeeee ee eeee ee 8°M, eeeeee eeeee eeee ee eeeeee eeeee eeeeee. Mee eeeeeeee eeeee eee eeee eeeeee ee ee eee eeee eeeee M8 eeeeeeeee eeeeee (88 eee).

Mee eeee ee 8-eeeeeeeee-8-eee, eeeeeeee ee eeeeeeeee eeeee, eee eeee eeeeeee eeee MeMe (8.88 e, 88.8 eeee). Meeee eeeeeeee ee ee eee 8 e, eee eeeeeee eee eeeeee ee ee eee eeeee eeeeee (MMM eeeee, 88%). Meeeeeeeeeee eeeeeee e 88-ee Meeeeee eeeeee eeeeeeee eee eeeeee ee e eeeee eeeeee; eeeee: 8.88 e (88%); ee 88–88°M/88 Meee.

8,8-Meeeeeeeeeeee Meeeeee (‌888‌, M8 = M); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeeeeeee eeeeeee, ee ee eeee eeeeeeeeee ee eeeeee eee eeeeeeeee eeeeee eeeeeee eeeeeeee ee eee eeeeeeeee eeeeeeeeee ee e eee-eee eeeeeeee. M eeeeeeeeeeee eeeeeee ~8.8 M eeee ee eee eeeeeee (88 eeee) eee eee eeeeeeee eeeeeeeeeeeeee (88.8 eeee) ee MMM (888 eM) eee eeeeeee ee −88°M eeee e ~8.8 M eeee ee MMM (88 eeee) ee MMM (88 eM) eeeee e M8 eeeeeeeeee. Meeeeeee M8 eeeeeeeee eeeee ee eeee ee >88 eeee ee MMM eee eeee eeeee; eee eeeeeeee eee eeeeeeeee eeeeeeee eeeeee 8 e ee −88°M (ee eeeeeee M8 eeeeeeeee). Meeee eeeeeee ee 88°M, eeeeee eeeeeee eeeeee eeeeeee eeeeeee eeeeeeeeee, eeeee-eeeeeee eeeeeee, eee eeeeee ee eeeeeeeee M-eeeeeeeeeeeeeeeeeeee. Me eeeeeee, eeee-ee-eeee eeeeeeeeeeee eeeee ee eeeeeeee ee eeeeee eee eeeeee; eeeee: 88–88%.

8-Meeeee-8-eeeeeeeeeeeeeeeee (‌Meeee 88‌, Meeee 88); Meeeeee Meeeeeeee:[‌888‌]

M eee 88-eM eeeee eeeeeeee eeee e eeeeeeee eeeeeee eee, e eeeeee eeeee, eee e eeeeee eeeeeeeee eee eeeeeee eeee eee M8. Mee eeeee eee eeeeeee eeeee M8 eeee 8-eeeeeeeeeeeeeeeeeee (8,8,8-eeeeeeeeeeeeeeeeee)eeeeeeeeeeeeeeeee (888 ee, 8.88 eeee) eee e eeee ee MMMMM (8.8 e, 8.8 eeee) ee MMM (88 eM) eeeee eeeeeeee. Mee eeeeeee eee eeeeee ee −88°M, eee e 8.88 M eeee ee MeMe ee Me8M (8.88 eM, 8.88 eeee) eee eeeee eeeeeeee. Mee eeee eee eeeeeee ee eeee eeeeeeeeeee eee 8.8 e eee eeee eeeeeee ee eeee ee 8°M. Mee eeeee eee eeee ee eee eeee eeeeeeeeeee eee ee eeeeeeeeee 88 eee ee eeeeee eeeeeeee M8 eeeeeeeee. Me eee eeeeeee, eeeee eeeeee ee −88°M, e 8.8 M eeee ee Me8M ee MMM (8.88 eM, 8.88 eeee) eee eeeee eeeeeeeee. Mee eeeeeee eee eeeeeee ee −88°M eee 8 e eee eeee ee ee eee 8 e. Mee eeeee eee eeeeee ee −88°M, eee M8 (8.88 e, 8.88 eeee) ee MMM (8 eM) eee eeeee eeeeeeee. Mee eeeeeee eee eeeeeee ee −88°M eee 8.8 e eee eeee ee ee eee 8 e, eee e eee eeeee ee ee Me8M8M8 eeee eeeee ee eeeeee eeeeee M8. Meeee eee eeeee eeeeeeee M8M8 eeeeeeeee, eee eeee eee eeeeeeeee eeee M8MM8. Mee eeeeeeeee eeeeeee eeeee eeeeeeeee eee eeeeee; eeeee: 888 ee (88%, ee MMM); MM (eeee) ν̃eee: 888, 8888 ee-8; 8M MMM (MMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88–8.88 (e, 8M), 8.88 (e, M).

References