Science of Synthesis

Schobert, R.; Gordon, G. J., Science of Synthesis, (2004) 27, 1027.

Several approaches have been used for the syntheses of carbocycles and heterocycles via ring-closing Wittig reactions:[‌459‌,‌490‌] (1) an intermolecular double condensation between a diylide and a reactant containing two carbonyl groups;[‌491‌–‌496‌] (2) intramolecular ring closures of reactive ω-carbonylated ylides, which can be generated in situ from more stable precursors (e.g., other ylides, phosphonium salts, or phosphines); and (3) the partial oxidation of diylides, followed by intramolecular Wittig alkenation. The intramolecular processes are particularly advantageous as they can be performed with functional groups normally less prone to Wittig alkenation, such as esters and amides.[‌182‌] Even strained ring systems, including annulated and bicyclic bridgehead cycloalkenes, can be formed as the phosphine oxide elimination step is strongly exothermic.[‌497‌]

Meeeeeeeeeee eeeeeeeeeeee eeeeeeeeeeee eeeeeeeeee eeeeeeee eeeeeeeeeeee ee eeeeeeeeeeee eeeee eee eeeeeeee ee eeeeee eeeeeeeeee eeeeeeee eeeee eeeeeee ee eeee eeeeeeeeeee eee eeeee (eeeeeeeee eeee eeee ee eeeeeeeee ee eeee). Mee eeeeeee, eeeeeeeee ee ω-eeeeeeeeeeeeeeeeeee eeeee ‌888‌ eeee eeeee (e.e., eeeeeeeee, eeeeeeeeeeeee, eeeeeeeeeeee, eeeeee eeeeeee, ee eeeeee eeeeeeeeeeeeeeeeeeeeee) eeeeeeeee eee eeeeeeeeeeeee eeeee, eeeee eeeeeeeee e eeeee eeeeeeeeeeeeee Meeeee eeeeeeeeee ee e eeeeeeeeeee ‌888‌ (‌Meeeee 88‌). Meee eeeeeeee eeeee eeeeeeeeeeeee eee eeeeeeeeeeee,[‌888‌,‌888‌] eee eeeee- eee eeee-eeeeeeee eeee eeeeeeee eeeeee ee eeeeeeee ee eeee eee. Meeeeeeeee eeeeeeeeeeeeee eeee ee ‌888‌ (‌Meeeee 88‌) eee eeeee ee ee eee eeeeeeeeee ee eeeeeeeeeeeeee ee eee eeee ‌888‌ eeee ee eeeeee eeee eee eeeeeeee ee eee α- ee β-eeeeeeee.[‌888‌] Meeeeeeeeee eeeeeeeeee eee eeee eeeeeeeeee eee eeeeeeeeeeeee eeee ee ‌888‌ eeee eeeee eeeeeeeeee eeee 88 ee 88 eeeee eee eeeeeeee ee eeeeee eeeeeeee eeeeeeeee ee eee eeeeeeeeeee ω-eeeeeeeeee eeeeeeeeeee eeeee ‌888‌ eeee e eeeeeeee eeeee eeeeeee eeeeee eeeeeee eeee eeeeeee, eeee eeeeeeee eee eeeeeeeee eeee eeeeeeee eeeeeeeeee eeeeeeee ee eeeee eeeeeeeeeeeee (‌Meeeee 88‌).[‌888‌,‌888‌–‌888‌] Meeee eeeeeeee eee eee eeeeeeeeeeeeeeee ee ω-eeeeeeeeeeee eeeeee eeee eeee eeee eeeeeeeee.[‌888‌,‌888‌]

‌Meeeee 88‌ Meeeeeeeeeee eeee Meeeeeeeeeeeeeeeeee Meeee eee Meeee[‌888‌–‌888‌]

Meeeeee eeeee ee eeeeeeeeeee eeeee- eee eeeeeeeeeeee ‌888‌, eeee ee eeeeeeeeeeeee,[‌888‌] 8M-8-eeeeeeeeeee,[‌888‌,‌888‌] eeeeeeeeeeeeee,[‌888‌] 8,8-eeeeeeeeeeeeeeeee,[‌888‌] eee., eeee eeee eeeeeeee eeee eeeeeeeee eeeeeeeeeeee ω-eeeeeeeeeeee eeeeee ‌888‌ eee eeeeeeeee(eeeee)eeeeeeeeeee eeeeeee[‌888‌] (‌Meeeee 88‌). Me eee eeeee eeee eee eeeeeeeeeee eeee ee eee eeeeeeee eeeeee eeee ee eee eeeee eeeeeee ee eeeeeeee e eeeeeeee ω-eeeeeeeeeeee eeeee, eeeee eeee eeeeeeeee e eeeee eeeeeeeeeeeeee Meeeee eeeeeeeeee eeeeeeee. Meeeeeee eeeeeeeeeeee eeee eeeeeee eeeeee, eeeeee, eeeee, ee eeeeeeee eeeeeee. Meee eeeeee eeee eeeee eeee eee δ-eeeeeeeeeeee eeeeee ee eee eeeee eeee, ee eeeee eeee eeeeeeeeeeeeee eeeeeeeeeee ‌888‌ (M = MM8; M = MMM8) eee eeeeee.[‌888‌] Mee eeeeeeeee ee eeeeeeeeeee eeeeeeeeeeeeeee eeee eeeee(eeeeeeeee)eeeeeeeeeee eeeeeee eee eee eeeeeeee ee M-eeeeeeeeeeee-α-eeeee eeeeeee eeee eeee eeee eeeeeeeee.[‌888‌] Meeeeeee, eeeeeee eeeeeee eee ee eeee ee eeeeeeeeeeee ee eeeeeee eeeeeeeee eeee (eeee-8,8-eeeeee)eeeeeeeeeeeeeeeeeeee eeeeeee (‌888‌) ee eeeee eeeeeeeee-8,8-eeeeee, eeee ee eee eeeeeeee eeeeeeeeee ‌888‌,[‌888‌] ee eeee eeeeeeee-8-eeeeeeeeeeeeeee eeeeeeeeeee ‌888‌ ee eeeeee eeeeeee[8.8.8]eeee-8-eeee ‌888‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeeeeee eeee Meeeeeeeeeeeeeee Meeee eee ω-Meeeeeeeeeee Meeeee[‌888‌–‌888‌,‌888‌–‌888‌]

‌Meeeeeeeeee 88‌

Meeeeeee ‌888‌	Meeeeee ‌888‌	Meeee (%)	ee (°M)/ee [(°M)/Meee]e	Mee
		88	888/888	[‌888‌]
		88	88–88/88	[‌888‌]
		88	88/8.8	[‌888‌]
		88	88–88	[‌888‌]
		88	88–88	[‌888‌]
		888	e.e.	[‌888‌]
		88	e.e.	[‌888‌]

e e.e. = eee eeeeeeee.

Meeeeeee ee eee eeee eeeee eeee eee ee eeeeee eeeeeee eeee eeeeeeee eeeeeeeeeeee ee eeee eee eeeeeeeeeeeee eeee-eeeeee ω-eeeeeeeeeeee eeee eeeeee eeee eeeeeeee eeeeeee eeeee Meeeee eeeeeeeeeeeee. Meee eeeeee eeeeeeee eee eeeee eee ee eeeeeee eeeeeeeee, ee ee eee eeeeeeeeee ee eee eeeeeee ‌888‌ eeee eee eeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] M eeeeeee eeeeeeee eeeeeeee eeee 8,8-eeeeeeeeee ‌888‌ (M = M) ee 8,8-eeeeeeeeeeee ‌888‌ (M = M) eee eeeeeeee eeeeee eeeee ee eee eeeeeeeeeeeee eeeeeeeeeee ‌888‌ (M = M) ee eeeeeeeeeeeeeee ‌888‌ (M = M), eeeeeeeeeeee (‌Meeeee 88‌).[‌888‌] Meeeeeee ω-eeeeeeeeeeee eeeeee eee eeee eeeeeeee ee eeeeee eeeeee eeeeeeee eeeeeeeeeeeeee Meeeee eeeeeeeeeee eeeeeee ee eeeeeeeeeee 8,8-eeeeeeeeeeeee ‌888‌ (M = M) eee 8,8-eeeeeeeeeeeeeee ‌888‌ (M = MM8) eeee α-eeeee ee α-eeeeeee eeeeee, eeeeeeeeeeeeeeeeee, eee eeeeeeee eeeeeeeeeeeeeeeeeeeeee (‌Meeeee 88‌).[‌888‌] Meee eeeeeeeee eeeeeeee ee eeeeeeee ee eee eeeeee eeeee (MM ee MMM8), eeeeeeeeeeee, eeeeee eee M≡M eeee ee eeee eeee eeeeee ee eeeeeeee, eeeee eeee eee ee eeeeeeeeeeeeeeeeee ee eeeee eeeeeeeeee eeeeee. Meeee ee eeee eeeeeee e eeeeeeeee Meeeee eeeeeeeeee. Me eeee eeeee eee/eeeee eeeeee eeeeeee eeee 8:8 ee 88:8 eee eeeeeeee. ω-Meeeeeeeeeee eeee eeeeee eee eeee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee ω-eeeeeeeeeeee eeeeeeee eee eeeeee ee eee eeeeeeeee eeeee (eeeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeeee (Me8M=M=M=M) (eee Meeeeee ‌88.88.8.8‌).

Meee-eeeeeeee ω-eeeeeeeeeeee eeeeee eeeeeee eeeeeeeeeeeeeee eeee ee eeeeeeee eeeeee, eeeeee, eeeeeeeeee, M-eeeeeeeeee, eeeeeeeeeeeeeeeee, eee., eeee eee ee eeeeeeeee ee eeee. Meee eee ee eeeeeeee eeee eeeeeee eeeeeee eee eee, ee eeee eeeee, ee eeeeeeee ee eeeeeeeeeeee Meeeee eeeeeeeeee eeeeeeeee eeeee eeeeeee eeeeeeeeee.[‌888‌] Meeeeeeee eeeeeeee eee eeeee ee eee eeeeeeeee ee (−)-eeeeeeeeee M eeee e eeeeeeee eeeeeee eeeeeeeeeee,[‌888‌] eee ee eeeee eee eeeeeeeeee β-eeeeee eeeeeeeeeee eeee M-eeeeeeeee eeeeee.[‌888‌] Meeee eeeeeeee eeee eeee eeee eeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeeeeee eeee ω-Meeeeeeeeeee Meee Meeeee Meeeeeeee Me Meee[‌888‌,‌888‌,‌888‌]

Mee eeeeeeeee ee eeeeeeee ‌888‌ eeee eeeeee ee eeeee eee eeeeeeeeeeeee M-eeeeeeeeeeee ‌888‌ (eee ‌Meeeee 88‌), ee ee eeeeeeeeeeeeee Meeeee eeeeeeeeee ee eee eeeeeeeee eeeeee ω-eeeeeeeeeeee eeeeee, eeeee eeee eeee eee eeeeeeee eeeeee eeeee eee eeee ee eee Meeeee eeeeeeee ee eeeeeee eeee eeee ee eee eeeeeeeee eeeeeee, eee eee eeee eeeee ee ee eeee eeeee. Meee eeeeeeeee eee ee eeeeeee eee ee eeeeee eeeeeeeeeeeeee ee e eeeeee eeeeeeeee (‌Meeeee 8‌), eeee eeeeee eee eeeee eeeeeeeeee ee e eeeeeeeeeee eeee eeeee eeeeeeeeeee ee eeeeeeee.[‌888‌] Mee eeee eee-ee ee eeeeeee eeeeee eee eeeeeeeeeeeeee eeeeeeee, eee eeeeeeee eee eeeeeeeee ee β-eeeeeeee eeee 8 eeeeeeeeeee ee eeeeeeeeeeeeeee(eeeeeeeee)eeeeeeeeeee.[‌888‌] Meeeeeee, eeeeeeeee ee eeee eeee eeeeeeee eeeeeeeeeee eeeeeeeeee ‌888‌, eeeeeee eeeeeee eeeeeeeeeeee ee eeee eeeeeeeeeeee (‌Meeeee 88‌).

‌Meeeee 8‌ Meeeeeeee eee eee Meeeeeeee ee Meeeeeee ee Meeeeeeeeeee[‌888‌,‌888‌]e

e Meeeeeeee eeee (Meeeeeee, Meeeeeeee Meeeeeeeee ee Meeeeeeee, Meeeeeeeeeeeeeee Meeeeeee, Meeeee, M., Me.), Meeeeeeee (8888), e 888, eeee eeeeeeeeee eeee Meeeee Meeeeeeeee Meeee.

‌Meeeee 88‌ Meeeeeeee ee M-Meeeeeeeeeee eeee eee Meeeeeeee ee Meeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

M	Meeeeeeeeee ‌888‌	Meeee (%) ee ‌888‌	ee (°M)/ ee [(°M/Meee)]e	Mee
(MM8)8	(M)-eeeeeeeeeeee	88	e.e.	[‌888‌]
(MM8)8	(M)-eeeeeeeeeee	88	e.e.	[‌888‌]
(MM8)8	(M)-eeeeeeeeeeee	88	e.e.	[‌888‌]
(MM8)8	(M)-eeeeeeeeeee	88	e.e.	[‌888‌]
	eeeeeeeeeeeeee	88	88–88	[‌888‌]
	eeeeee	88	88/88	[‌888‌]
	8,8-eeeeeeeeeeeeeeeeee	88	88/88	[‌888‌]
	8M-eeeeeee[e,e]eeeeeeeeeeeeeeee	88	888	[‌888‌]
	8,8-eeeeeeeeeeeeee[e,e]eeeeeeeeeeeeeeeee	88	888	[‌888‌]

e e.e. = eee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

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

Mee eee eeeeeeeeeee eeee ‌888‌ (8.88 e, 88.8 eeee), eeeee eee eeeeeeee ee ee eeeeeeeee eeeee ee eeeeeee eee eeeeeeeeeeeee eee eeeeeee eeee Me8M (8 eeeee) ee eeeee Me8M ee 888°M, eee eeeeeeeee ee eee eeeeeeeeeeeee eeeeee eeeeeeee eeeee (88 eM) eeeeeeeeee 8-eeeeeeeeeee-8-ee (8 eeeee). MeM (888 ee; 8.8 eeeee) eee eeeee eee eee eeeeeee eee eeee eeeeee ee 88°M eee 88 eee. Mee eeeeeeeeeee ee eee eeeeeee eee eeeeee ee 888°M eee eee eeeeee eeeeeeeee ee 88 Meee ee ee eee eeeeee. Mee eeeee eeeeee-eeeeeeeee eeeeeee eee eeeeeeeee ee eeeeeee, eeeeee eeee M8M, eeeee (Me8MM8), eee eeeeeeeeeee; eeeee: 888 ee (88%); ee 88–88°M.

8M-Meeeeeeeeee (‌888‌, M8 = M; M,M = M=MMMM=MMM); Meeeeee Meeeeeeee:[‌888‌]

Meeeeee-8-eeeeeeeeeeee (88.8 e, 888 eeee) eee eeeee ee e eeeeeeeeee ee MeM (8.8 e, 888 eeee; 8.8 e ee e 88.8% eeeeeeeeee ee eeeeeee eee) ee eeeee Me8M (888 eM). Meee eee eeeeeeee eee eeeeeeee, eeeeeeeee(eeeee)eeeeeeeeeee eeeeeee (88.8 e, 888 eeee) eee eeeee. Mee eeeeeee eee eeeeeee eee eeeeeeee eee 88 e, eeeee eeeee eeee eee eeeee eeee eeeeeee ee eeeeeeeeee eee Me8M eee eeeeeeeee eee. Meeeeeeeeeee ee eee eeeeeee eeee 8M-eeeeeeeeeee, eeeee eeeeee eeee eee eeee ee e Meeeeeee MM eeeeee (88 e, 888°M); eeeee: 88.8 e (88%); ee 88–88°M/88 Meee. Meeeeeeeeeeeee eeee ee eeeeeeeeee eeeeee: ee 88°M/8.8 Meee.

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

8,8-Mee(eeeeeeeeeee)eeeeeeeeeee (8.8 e, 88.8 eeee) eee Me8M (88.8 e, 88.8 eeee) ee eeeeeee eeeeeeeee MMM (88 eM) eeee eeeeeee eee eeeeee ee 888°M eee 8 e, eeeeeeeee eeeeeeeeee eeeeeee ee e eeeeeeeeeee eeee eeeeeeeeeeee. Meee eeeeeee eee eeeeeee eeeeeeeee ee eeeeeeeeee ee eee eeeeee eeeeeee eeeeeee e Müeeeee eeeeee eee eeeeee eeeeeeeeee eeee 888 eM eeeeeeee ee eee eeeeeee ee eeeeee eeeeeeee Me8M. Me eee eeee eeeee eeeee eeeeeee eeeeeeee ee eeeeee 8,8-eee[eeeeee(eeeeeeeee)eeeeeeeeeee]eeeeeeeeeee eeeeeeeee ee e eeeeeeeeeee eeeeeeeee eeeee; eeeee: 88.8 e (88%); ee 888–888°M (eee).

M eeeeeee ee MeM (8.88 e, 88 eeee) eee eee MMMM (888 eM) eee eeeeee ee e eeeee-eeeeee eeeee ee eee eeeeeeeee eeeee ee ‌Meeeee 8‌ eee eeeeeeeeee eeeee ee eeeeeeeeee ee eee M8, eeeee eeeee eeeeeee eee eeeeee eeeeee ee 88–88°M. (MMMMMMM: Me eee eeeeeeee eeee eeeeeee ee eeee ee ee eee eeeeeee. Meeeeeee eeeeeeeeeeeee eee eeeee eeeeee 888°M.) Meee eee eeeeeeeee ee M8 eee eeeeee (ee. 8 e), 8,8-eee[eeeeee(eeeeeeeee)eeeeeeeeeee]eeeeeeeeeee eeeeeeeee (88.8 e, 88 eeee) eee eeeee. Meee e eeee eee eeeee eeeeeeeee eee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee, eee eee eeeee eeee eee eeeeeeeee ee ee M8 eeeeee eee eee eeeeee eee-ee eee eeeeeeeeee eeeeeee eeee eee M8, eeeee eeeeeeeeeee eee eeeeeee ee 88–88°M. Mee eeeee eee eee eeeeee eee eee M8 eeeeeeeeee eee eeeeeeeeeeee eeeeeeeeee eeeeeee eee eeeeeee ee eeeee ee e eeeeeeeeeee eeee. Meeee eee eee eeee, eee eeeeeeeee eee eeeeee eeee eeeee M8. Meeee 8 e, eee eeeee ee eee eeeeeee eee eeeeeee ee eeeee eee eeeeeeeee eee eeeeeeee. Mee eeeeeee eee eeeeee ee ee, ee eeeeee ee M8M eee eeeee, eee eee eeeeeeeeeee eeee eeeeee eee eeeeeeeee, eee eeeeeeeeee eeeeeeeee eeee eeeeeeee ee eee eeeeeeeee eeeee (88 eM). Mee eeeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeeeee eeeeeee eee eeeeeeee ee eeeeeeeeeee ee 88–88°M/8.8 Meee ee eeeeee eeeeeeeee eeeeeeee; eeeee: 8.8 e (88%); ee 88–88°M.

References

Meeeeee Meeeeeeeeee

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