Science of Synthesis

Kostikov, R. R.; Khlebnikov, A. F.; Sokolov, V. V., Science of Synthesis, (2010) 47, 854.

The Bamford–Stevens reaction has been widely used for the synthesis of various mono- and oligocyclic unsaturated compounds. Usually this transformation of ketones into alkenes proceeds without changes in the constitution of the carbon skeleton. However, if the target alkene is unstable at high temperature or toward strong bases, this method furnishes mixtures of isomeric alkenes. In such cases it is preferable to employ the Shapiro protocol, i.e. transform the tosylhydrazone into a metal salt and decompose the latter. If the intermediate carbene contains an α-cyclopropyl group or if the carbenic center is enclosed in a ring-strained carbon skeleton, rearrangements may occur.

(+)-Meeeeeeeee eeeeeeeeeeeeee (‌888‌) eeee eeeeeeeee eeee eeeeeeeeeeee eeeee eee M-eeeeeee eeee, eeeee eeee eeeeeeeeeee eeeeeeee e eeeeeee ee Δ8-eeeeeee (‌888‌) eee eeeee- eee eee-Δ8-eeeeeeee (‌888M‌ eee ‌888M‌) ee 88% eeeee, eeee ‌888‌ ee eee eeeee eeeeeeeee (88%) (‌Meeeee 88‌).[‌888‌,‌888‌] Meeeeeeeeeeee ee eee eeeeeeeeeeeeee ‌888‌ eeee e eeeeeeee ee eeeeee ee eeeeeeeee ee 888–888°M eeeeeeee e eeeeeeeeeee eeeeeee (88% eeeee) eeeeeeeeee ee ‌888M‌ eee γ-eeeeeeeee (8:8), eeeee eee ee eeeeeeeee ee eeeeeeeeeee eeeee-eeeee eeeeeeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee e Meeeeee ee (−)-Δ8-Meeeeee eee eeeee- eee eee-Δ8-Meeeeeee[‌888‌]

8α-Meeeeee-8-eee (‌888‌) ee eeeeeeee eeee eee eeeeeeeeeeeeee ‌888‌ ee 88% eeeee (‌Meeeee 88‌).[‌888‌] Meeeeee eeeeeeee eee eee eeeeeeeeee ee eeeeeee eeeeeee (e.e., ‌888‌), eeeeee, eee eeeeeeeeeee eeeeeee eee eeeeeeeee ee ‌Meeee 88‌.[‌888‌–‌888‌] Meeeeeeeeee ee M-(8-eeeeeeeeeeeeeeee)eeeeeeeee ee 888°M eeeeeee eeeeeeeeee eeeeeeeee eeeeeeeeeeeeee eeeeeee eeeee eeeeeeeeeee eeeeeee eeeeeeeeee. Meee eeeeeeeeeeeeeeeeeeeeeeeeee ee eeeeeeee ee 88% eeeee.[‌888‌] M eeeeeeeee eeeeeeeee eeeee eeeeeeeee eeeeeeeeeeee ee e eeeeeeee eee eeee eeeeeeeee eee eee eeeeeeeee ee eeeeeee eeee eeee eeeeeeeeee. Meeeeee e 8% eeeeeee eeeeeeee ee 8,8-eeeeeeeeeeeeeee-8-eee M-(8-eeeeeeeeeeeeeeee)eeeee ee 888°M eee 8–8 eeeee eeeee eeeee ee eee eeeeeeee ee 8 eee% ee eeeeeee(MM) eeeeeee eeeee eeeee e eeeeeee ee 8,8-eeeeeeeeeeeee-8-eee eee 8,8-eeeeeeeeeeeee-8-eee ee e eeeee ee 88:88 (eeee ee e eeeeeee ee eeeeeeeeeeeee).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee 8α-Meeeeee-8-eee[‌888‌]

‌Meeee 88‌ Meeeeeeee ee Meeeeee eeee Meeeee (Meeeeeeeeeee)eeeeeeeeee ee eee Meeeeee–Meeeeee Meeeeeee[‌888‌–‌888‌]

Meeee	Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeee(e)	Meeee (%)	Mee
8		MeMe (8 eeeee), Meeeeee, 88–88°M		888	[‌888‌]
8		MeMe (8 eeeee), Meeeeee, 88–88°M		888	[‌888‌]
8		MeMM8, Meeeeee, 888°M		88	[‌888‌]
8		MeMe (8 eeeee), Meeeeee, 88–88°M		888	[‌888‌]
8		Me, eeeeeeee eeeeee, 888°M		88	[‌888‌]
8		Me, eeeeeeee eeeeee, 888°M, 8.8 e		888	[‌888‌]
8		MM8, Me8MMe, MMM, 88°M, 8–8 e		88	[‌888‌]
8		MeMMe, MMM, 888°M, 88 eee		88 + 88	[‌888‌]
8		MMM, 888°M		88 + 88	[‌888‌]
88		MM, MMMM, 888°M		88e	[‌888‌]
88		Me, eeeeeeee eeeeee, 888°M		88	[‌888‌]
88		MeMMe, 888–888°M		88–88	[‌888‌]
88		MeMMe, eeeeee-8,8-eeee, 888°M		88e	[‌888‌]
88		Me, eeeeeeee eeeeee, 888–888°M, 8.8 e		88	[‌888‌]
88		MeMMe, eeeeeee, 888°M		88e + 88e	[‌888‌]
88		Me, eeeeeeee eeeeee, 888°M, 8.8 e		88 + 88	[‌888‌]
88		e-MeMM, MMM, 888°M, 8.88 e		88 + 88	[‌888‌]
88		e-MeMM, MMM, 888°M, 88 eee		88 + 88	[‌888‌]

e Meeeeeeeeeeeeeeeeeeeee (88%) eee eeee eeeeeeee.

e Meeeeee ee 88% M- eee 8% M-eeeeeee.

e Meeeeee ee eeeeeeeeeeeee.

Mee eeeeeeee ee 8,8-eeeeeeeeeeeee-8-eee eeeeeeeeeeeeee eeee eeeeee eeeee 8,8-eeeeeeeeeee-8-eee, eee eeeeeee ee e 8,8-eeeeee eeeeeeeee (‌Meeee 88‌, eeeee 8).[‌888‌] Meeeeeeee, eee Meeeeee–Meeeeee eeeeeeee ee eeeeeeeeeee eeeeee eeeeeeeeeeeeeee ‌888‌ eeeee eeeeeeeeeee eeeeeeeeeee ‌888‌ ee eeeeee ee e eeee-eeeeeeeee 8,8-eeeee eeeeeeeee ee eee eeeeeeeeeeee eeeeeeeeeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] Mee eeeeeeeeeeeee ee eeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeee eeeeeeeeeeeeee (‌888‌, M8 = M) ee 8-eeeeeeeeeeeeeeee-8-eee ee 888°M eeeee eeeeeeeeeee (88%), eeeeee (88%), eee eeeeeeeee (88%).[‌888‌] Me eeee eeeee, eeeeeeeeeeeeeeeeee eee eeeeee eeeee eeee eee eeee-eeeeeeeeeee eeeeeeee; eee eeeeeee eeeeeeeeeeee eeeeeee ee eee eeeeeeeeee eee eee eeeeeeeeeeee ee eee eeeeeee eeeeeeeeeeeee. Meeeeee eeeeeeeeeee eeeeeeeee eee eeeee ee ‌Meeee 88‌, eeeeeeeee eee eeeeeeeee ee eee eeeeeeee eeeeee ‌888‌.[‌888‌–‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeee eeee Meeeeeeeeee Meeeee Meeeeeeeeeeeeee[‌888‌,‌888‌]

‌Meeee 88‌ Meeeeeeeeee Meeeeeee eeee eee Meeeeee–Meeeeee Meeeeeee ee Meeeeeeeeee Meeeee eee Meeeeeee Meeeeeeeeeeeeee[‌888‌–‌888‌]

Meeeeeee Meeeeeee	Meeeeeeeee	Meeeeee(e)	Meeee (%)	Mee
	MeMMe, ee(eeeeeeee eeeeee) eeeeeee eeeee, 888°M		88e	[‌888‌]
	MeM, eeeeeee, 888°M		88	[‌888‌]
	MeMMe, 8,8,8-eeeeeeeeeeeeee, 888°M		88	[‌888‌]
	MeMMe, 8,8,8-eeeeeeeeeeeeee, 888°M		88	[‌888‌]
	MM, MMMM, 888°M		8 + 88e	[‌888‌]
	MM, MMMM, 888°M		88e	[‌888‌]
	MeM, eeeeeee, 88–888°M		88	[‌888‌,‌888‌]
	MeM, eeeeeee, 88–888°M, 8 e		88	[‌888‌]
	MeMe, MMM, 88–888°M, 8.88 Meee, 88 eee		(88:88)e	[‌888‌]
	MeMMe, 888–888°M, 888 Meee		88 + 8	[‌888‌]
	MeMe, MMM, 88–888°M, 8.88 Meee, 88 eee		(88:88)e	[‌888‌]
	MeM, eeeeeee, 888°M		88	[‌888‌]
	MeM, eeeeeee, 888°M		88	[‌888‌]

e Meeee ee eeeeeeee; eeeee eee eeeeeeee.

e Meeeeeee eeeeeee eeeeeeeee eeee eeeeeeee eeeeee (88–88%).

Mee Meeeeee–Meeeeee eeeeeeeeeee eee eeee eeee eee eee eeeeeeeee ee eeee-Meeee eeeeeeeeeeeeee. Mee eeeeeee eeee ee eeeeeeeee-8-eee eeeeeeeeeeeeee eeeeeeeee eeeeeeeeeee ee 888°M ee eeee e 8-eeeeeeeeeeeeee, eeeee eeeeeeeeee ee eeeeeee[8.8.8]eeee-8-eee (88% eeeee).[‌888‌] Meeeeeeee, eeeeeeeeeeee eee-eeeeeeee[8.8.8.88,8]eeeee-8-eee eeeeeeeeeeeeee (‌888‌) eeee eeeeeeeeeee eeeee eee eeeeee eeeeeeee eee eeeeeeee eeeeeeeee eeeeee ‌888‌ ee 88% eeeee (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeee[8.8.8.88,8]eee-8-eee[‌888‌]

Meeeeeeeeeeeeeee eeeeeeee ee eeeeee eeeeeeeeeeeeeee ‌888‌ eeeeeee ee eeeeeeeeee eeeee ee eee eeeeeeee ee eeeeee ee e eeeeeee eeeeeee ee eeeeeeeeeeeeeeeee eeeeeee eeeeeee ‌888‌ ee eeee eeeeee (‌Meeeee 88‌); eeee eee eeeeeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeeee eeeee 8-eeeeeeeeeeeeeeeee ee 88% eeeee.[‌888‌] Meeee eeeeeeeee eeeeeeee eee eee eeeeeeeeeeeee ee eeeeeeeeeeeeeee ee eeeeeeeeeeeee eee 8-eeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeee ee eeeeeeeeeeeeeeeee ee 88°M eee 8–8 eeeee eeeeeeeee eeeeeeeeeee (88%) eee 8-eeeeeeeeeeeeeeeee (88%).[‌888‌]

‌Meeeee 88‌ Meeeeeeeeeeee ee Meeeee Meeeeeeeeeeeeee ee e Meeeeee Meeeeee[‌888‌]

Mee eeeeeee eeeeeeeeeeeee eeeeeeee ee eee Meeeeee–Meeeeee eeeeeeee eeee eeee eeeeee eeee eeeeeeee ee eeeeeee eeeeeeeeeeee. Meeeeeeee ee eee eeeeeeeeeeeeeeeeeeeeee eeeeeeeeeeeeee eeeeee eeee ee eeeeeee eeeee 8-eeeeeeeeeeeeeeeeeeeeee ee eee eeeee eeeeeee (eee ‌Meeee 88‌), eeeee eeee eeeeeeeeeeeeeeeeeeeeee ee e eeeee eeeeeeeee (88%).[‌888‌,‌888‌] M eeeeee eeeeeee eeeee ‌888‌ ee eeee eeeeeeee ee 88% eeeee eeee eeeeeee eee eeeeeeeeeeeeee ‌888‌ eeee eeeeeeeee eeee-eeeeeeee eee eeeeeeee ee eeeeeeeeeeeeeeeee ee 888°M eee 88 eeeee (‌Meeeee 88‌). Mee eeeeeeeeeeeee ee eeee eeeeeeeeeee ‌888‌ eee eee eeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeeeee ee 8,8,8-Meeeeeeeeeeeeeee[8.8.8]eeeeee-8-eee Meeeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Δ8-Meeeeee (‌888‌), eeeee-Δ8-Meeeeee (‌888M‌), eee eee-Δ8-Meeeeee (‌888M‌); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee eeeeeeeeeeeeee ‌888‌ (8.88 e, 88.8 eeee) ee eeeee MMM (88 eM) eee eeeeeee eeee e 8.8 M MeMe ee eeeeee (88.8 eM, 8.8 eee) ee ee eeeee eeeee. Meeee eee eee eeee eee eeee eeeeeee eee 8 e, eeeeeeeeee 8.8 M eeee ee MeMe ee eeeeee (88.8 eM, 8.8 eee) eee eeeee eeeeeeee. Meeee eeeeeeee eee e eeeeeee 88 eee, eee eeee eee eeeeeee eeee M8M (8 eM) eee eee eeeeeee eee eeeeeeeee eeee eeeeeee (8 × 88 eM). Meeeeeeeeeeee ee eee eeee eee eeeeeeeeeeee ee eee eeeeeee ee 888°M eeeeeee e eeeeeee ee eeeee- eee eee-Δ8-eeeeeee eee Δ8-eeeeeee ee e eeeee ee 8:88:888 (8M MMM); eeeee: 8.88 e (88%). Meeeeeeeee ee eeeeeeeeeeee eeee e eeeee eeeeeeee-eeee eeeeee eeee eee Δ8-eeeeeeee (ee 888–888°M/888 Meee) eee Δ8-eeeeeee (ee 888–888.8°M/888 Meee) (88% eeee ee MM).

Meeeeeeeeeeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeee eeeee eeeeeeeeee eeeeeee ee eeeeeeee ee eeeeeee ee eeeeeeee ee eee eee eee eeee ee e eeeeee eeeeeeee.

M eeeeeeeeee ee MeMM8 ee eee MM8 eee eeeeeeee ee eeeeeeeeee Me (8.8 e, 888 eeee) ee eee MM8 (888 eM) eeeeeeeeee Me(MM8)8 (8.8 e). Meeeeee (888 eM) eee eeeee, eee eee MM8 eee eeeeeee ee eeeeeeeee. Mee eeeeeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeeee (88 e, 88 eeee) eee eeeee, eee eee eeeeeee eee eeeeee ee 888°M. Mee eeeeeeeee eeeeee eeee eeeeeeeee eee ee eee eeeeeee eee eeeeeeeee eeeee ee eeeeeeeee eee eee eeeeeeeee eee eeeeeeeeeee (ee ee. 88°M) ee eeee e eeeeeee ee eeeeeeeeeeeeeeeee eee 8-eeeeeeeeeeeeeeeee ee e eeeee ee 88:8 (ee 8M MMM); eeeee: 8.88 e (88%). Mee eeeeeeeeeeeeeeeee: 8M MMM (888 MMe, MMMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (ee, M = 88, 8 Me, 8M), 8.88 (ee, M = 88, 8 Me, 8M), 8.88 (eee, M = 88, 88, 8 Me, 8M); 88M MMM (888 MMe, MMMe8, δ): 8.88, 88.88, 888.88, 888.88.

eee-8-Meeeeeeeeeeee[8.8.8]eee-8-eee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeee eeeeee ee MeM (8.88 e, 88.8 eeee) ee eeeee eeeeeee (888 eM) eee eeeee eee-8-eeeeeeeeeeeee[8.8.8]eeeeee eeeeeeeeeeeeee (8.88 e, 88.8 eeee) ee eee eeeeeee eeeee M8. Mee eeeeeee eee eeeeee ee 888°M eeeee eee eeeeeeeee eeeeee, eeee eeeeee ee 8°M, eee eeeeee eeee eee-eeee M8M eee eeeeeee (8:8). Mee eeeeeeeee eeeeeee eeeee eee eeeeeeeee eeee eeeeeee, eee eee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee M8M, eee eeeee (MeMM8). Mee eeeeeee eee eeeeeeeee eeeeeee ee ee eeeee eeeee-eeeeeeeee eeeeeeee ee eeee e eeeee eeeeeeeee eee; eeeee: 8.88 e (88%); ee 88°M/88 Meee. Meeee-eeeee eeeeeeeeeeeeeee eeeeeeee eeeeee eee eeeeeeee ee eee eeeeeeeee ee e eeeee ee 8:88, ee eee eeeee ee eeeeeeeeee eeeeeeeee eeee. Mee eeeee eeeeeeeee eee eeeeeeee ee eeeeeeeeeee eeeee-eeeee eeeeeeeeeeeeee eee eeeeeeeeee ee eee eeeeeee eeeeeee; MM (eeee) ν̃eee: 8888, 8888, 8888, 8888, 888 ee-8; 8M MMM (MMe8, δ): 8.88 (e, 88M), 8.88 (e, M = 8.8 Me, 8M), 8.88 (e, 8M), 8.88 (e, M = 8.8 Me, 8M).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 88e8, 888.
• 8.Meeeee-Meee, (8888) M 8e, 888.
• 8.Meeeee-Meee, (8888) M 8e, 8.