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3.5.4 Conia-Ene Reaction

DOI: 10.1055/sos-SD-203-00165

Watson, I. D. G.; Toste, F. D.Science of Synthesis: Stereoselective Synthesis, (20113288.

The thermal cyclization of ketones onto a tethered alkene or alkyne is known as the Conia-ene reaction.[‌100‌] The reaction is a variant of the ene reacton, and is thought to occur as a six-electron process, involving an enol hydrogen shift, followed by a concerted cyclization (Scheme 46).

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Meeee eee ee-eeeeeee eeee eeeeeeeee ee eeeeeeeeeeeeeeee eeeeeee ee eee eeeeeeeeeee ee β-eee eeeeee eeee eeeeeee ee eeee α-eeeeeeeee eeeeee eeeeeeee.[‌888‌] Meeeeeee eeeeeee eeeeeeee eeee eeeeee eeee(M) eeeeeeeee eeee eeeeeeeeee, eee eee(eeeeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee(MM) eeeeeee ee (M)-88 [(M)-MMMM-MMMMMMM] eeeeeee eee Meeee-eee eeeeeee ee eeee eeeeeeeeeeeeeeeeee, eeeeee eeee eee eeeee. Mee eeeeeeee ee 88 eeeeeeeeeee ee eeeeee eeee eee eeeeeeeee(MMM) eeeeeeeeeeeeeeeeeeeeeeeee (88eee%) ee eeeeeee eeeee eeeeeee ee eeee eeee eeeeee eee eeeeeeeeeeeeeeeeeeee (Meeeee 88). Mee eeeeeeee eeeee eee e eeeee ee β-eeeeeeeeee eeeeeeeee (88 eeeeeeee, 8888% ee). Mee eeeeeee, eeeeee eee eeeeeeeee, eeeeeeee eeee-eeeee eeeeee eeeeeee eeeeeeee eeeee eeeeeeeeeeeeeeeeee. Mee 8-eeeeeeeeee eeeeee 888 (M8=8-MM8M8; M8=MMe) eeeeeeeee 888 (M8=8-MM8M8; M8=MMe) eeee 88% eeeeeeeeeeee eeeeee. Meeeeeeeee eeeeeeee ee 888 (M8=8-MM8M8; M8=MMe) ee Meee eeeeeeeeee eeeeee e eeeeee eeeeeeeeeeeeeeeeee eeeeeeeeeee eeee eee eeeeee, eeeeeeeee ee e eeeeeeeee eeeeee. Me eeeeeeee, eee eeeeeeeee eeeeee 888 (M8=Me; M8=MMe) eee β-eeeeeeee eeeeeeeee 888 (M8=Me; M8=Me) eeeeeee eeeeeeeeeee eeee eeeeeeeeee eeeeeeeeeeeeeeeeee (Meeeee 88). Mee eeeeeeee ee eeeeeee ee eeeee ee eee eeeeeeeeee ee e eeeeeeeee eeeeeee eeee eeee eeeeeeeee Meeee eeee eeeeeeee eeeeeeee ee eee eeeeee.

Meeeee 88 Meeeeeeee(MM)-Meeeeeeee Meeeeeeeeeeeeeee Meeee-Mee Meeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meee (e) ee (%) Meeee (%) Mee
Me MMe 88 88 88 [‌888‌]
8-MM8M8 MMe 88 88 88 [‌888‌]
8-eeeeeeee MMe 8 88 88 [‌888‌]
Me MMe 8 88 88 [‌888‌]
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Meeee 8 Meeeeeeee(MM)-Meeeeeeee Meeeeeeeeeeeeeee Meeeeeeeeee ee Meeeee-8,8-eeeeee[‌888‌]

Meeee Meeeeeeee M Meee (e) Meeeeee ee (%) Meeee (%) Mee
8 (M)-MMMM-MMMMMMM [(M)-88] 88 88 88 [‌888‌]
8 (M)-MMMM-MMMMMMM [(M)-88] 8 88 88 [‌888‌]
8 (M)-MMMM-MMMMMMM [(M)-88] 88 88 88 [‌888‌]
8 (M)-MMMM-MMMMMMM [(M)-88] 88 88 88 [‌888‌]
8 (M)-Meeeeeeee [(M)-888] 8.8 88 88 [‌888‌]
8 (M)-Meeeeeeee [(M)-888] 8.8 88 88 [‌888‌]
8 (M)-Meeeeeeee [(M)-888] 8.8 88 88 [‌888‌]
8 (M)-Meeeeeeee [(M)-888] 8.8 88 88 [‌888‌]

Meee eeeeeeeee-eeeeeeeee eeeeeeeeeee eeeeeeee ee e eee eeee ee eee eeeeeeeeee eeeee eeeeeeeee ee ()-eeeeeeeeeeeee, e eeeeeee eeeeeeeeeeee-eeee eeeeeeeeeeeee. Meeeeeeeee ee eee eeee eeeeee eeee (M)-eeee eeeee 888, eeeeeeee ee eeeeeeeee(MM)-eeeeeeeee eeeeeeeeeee eeeeeee eee eeeeeeeeeeee 888 ee 88% eeeee eee eeee 88% eeeeeeeeeeee eeeeee, eeeee eee eeee eeeeeee eeeeeeeeeee eeee eee eeeeeee eeeeeee 888 (Meeeee 88).

Meeeee 88 Meeee Meeeeeeee ee ()-Meeeeeeeeeeee ee Meeeeeeee(MM)-Meeeeeeee Meeeeeeeeee[‌888‌]

M eeeeeeeee eeeeeeee eee eeeeeeeeee ee Meeee eee ee-eeeeeee, eee eeee eeeeeeeee e eeeeeeeeeee eeeeeeee eeeeee eee eee eeeeeeeeee Meeee-eee eeeeeeee.[‌888‌] Mee eeeeeʼe eeeeeeee-eeeeeee eeeeeeeeeeee eeeeeeeee eee eeeeeeeee ee eeeeeeeeee eeeeeeee eeee β-eee eeeeee 888, ee eeee eeeeeeeeeeeeeeeeeeeeee 888. M eeeeee ee Meøeeeee eeeeMeeee eeee eeeeeeeeeeee eeee eeee eeeeeeeee, eee eee eeeeeeeeeee ee eeeeee(M) eeeeeeeeeeeeeeeeeeeeeeeee eeee eee ee eee eeeeeeeeeeee 8-eeeee-8-eeeeeeeeeeeeeeee-eeeeeee eeee eeeeeeeee 888 ee 888, ee e 88:8eeeee eeeee, eeeeee eeeeeee eee eee eeeeeeeeee eeeeeeee. Meee eeeeeeeeee eee eeeeeeee eee eeeeeeeee eeeeeeee, eeeee eeeee ee ee eeeeeeee eeee eeee eee eeeeeeee eeeeeeeeeeee. Mee eeeeeeee eeeeeeeee eeeeeeee eeee ee eeeeeeeee eeeeeeeeeeeeeeeeee eee e eeeee ee β-eee eeeeee (Meeeee 88).

Meeeee 88 Meeeeeeeee Meeee-Mee Meeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meeeee Meee (e) ee (%) Meeee (%) Mee
Me MMe 888 8.8 88 88 [‌888‌]
8-MeMM8M8 MMe 888 88 88 88 [‌888‌]
8-MM8M8 MMe 888 8 88 88 [‌888‌]
8-MeM8M8 MMe 888 8 88 88 [‌888‌]
8-eeeeeeee MMe 888 8 88 88 [‌888‌]
Me MMe 888 8.8 88 88 [‌888‌]
Me MMMe 888 8 88 88 [‌888‌]
MMe Me 888 8 88 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeee-8-eeeeeeeeeeeeeeeeeeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeeeeeeeee eeee eeee e eeeeeeee eeeeeee eee eee eeeee eeeeeeeee 888 (8888ee, 8 eeeee), Me8M (ee eeee e 8.88M eeee), eeeeeee MeMM (88 eeeee), eee Me(MMe)8 (88eee%) eeeeeeee ee Me{(M)-MMMM-MMMMMMM)}(MMe)8 (88eee%). Mee eeeeeeee eee eeeeeeeee ee MMM eeeee eee eeeeeeee eeeeeeee eee eeeeeeee. Mee eeeeeee eee eeeeeeeeee eee eee eeeeee eeeeeee eee eeeeeeeeeeeeeee (eeeeeee/MeMMe) ee eeee eee eeeeeeee eeeeeee.

8-Meee-8-eeeeeeeeeeeeeeeeeeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

M eeee ee eeeeeeeee 888 (8.88eeee), MeMM (8 eeeee, 88µM), eee Me{(M)-MMMM-MMMMMMM)}(MMe)8 (88eee%) ee Me{(M)-Meeeeeeee}(MMe)88M8M (8eee%) ee Me8M (8eM) eee eeeeeee eeeee eee eeeeeeee eee eeeeeeee ee eeeeeeeeee ee MMM. Mee eeeeeee eee eeeeeee eee eee eeeeeee eee eeeeeeee (eeeeee eee) ee eeee eee eeeeeeee.

8,8-Meeeee-8-eeeeeeeeeeeeeeeeeeeeee 888; Meeeeee Meeeeeeee:[‌888‌]

Me e eeee ee [MeMMe]8eeeeeee (8.8ee, 8.888eeee, 8.88eeee MeMMe) eee eeeeeeeeee 888 (88ee, 8.88eeee) ee eee MM8Me8 (8eM) eee eeeee β-eee eeeee 888 (8.8eeee). Mee eeeeeee eee eeeeeee ee ee eeeee eeeeeeee eeeeeeeeeee ee eee β-eee eeeee eee eeeeeeeee ee MMM. Mee eeeeeee eee eeee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeeee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee.

References