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1.2.2.30 γ,δ-Unsaturated Ketones from Allylation of Enolates and Enolate Equivalents

DOI: 10.1055/sos-SD-001-00083

Friesen, R. W.Science of Synthesis, (20011181.

Ketone enolates react with allyl electrophiles under palladium catalysis to give monoallylation products, presumably by alkylation of initially formed electrophilic η3-allylpalladium complexes. The range of enolate cationic counterions, electrophiles, and palladium catalysts that are effective in carrying out this transformation are numerous, as exemplified by the cyclohexanones 314 obtained from the allylation reactions of cyclohexanone enolates 313 (Scheme 75, Table 5).

Meeeee 88 γ,δ-Meeeeeeeeee Meeeeee eeee Meeeeeeeee ee Meeeeeee[‌888‌‌888‌]

Meeee 8 γ,δ-Meeeeeeeeee Meeeeee 888 eeee Meeeeeeeee ee Meeeeeee 888

Meeee M8 M8 M Meeee Meeeeeeeeeee (M8-M) Me Meeeeeee Meeee (%) Mee
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8 M M Me Me(eee)8/eeee 88 [‌888‌]
8 M M Me Me(eee)8/eeee 88 [‌888‌]
8 Me M Me Me(MMe8)8 88 [‌888‌]
8 M M MeMMe8 Me(MMe8)8 88 [‌888‌]
8 M Me MMMe8 Me(MMe8)8 88 [‌888‌]
8 Me M MMMe8 Me(MMe8)8 88 [‌888‌]
8 Me M MeMe Me(MMe8)8 88 [‌888‌]
8 M M MeMe8 Me(MMe8)8/eeee 88 [‌888‌]
88 M Me MeMe8 Me(MMe8)8 8888 [‌888‌]
88 M Me MeMe8 Me(MMe8)8 88 (M) [‌888‌]

Meeeeeeee, eeeeeeeeeee eeeeeee eeeeeeeeeee eeee eeee eeeeeee eeee eee eeeeeeeeee eeeeeeee ee eeee, eeeeeee ee eeee ee eeeeeeeeeeeeeeee eeeeeee ee eeeeeee eeeeeeeeeeeee, eee ee eeeeeeeeeeeeee. Me eeeeeeee ee eeeeeeeeeee eeeeeeeeee eeeeeeeee, eee eeeeeeeee-eeeeeeeee eeeeeeeee ee eeeee-[‌888‌,‌888‌,‌888‌] eee eee-[‌888‌,‌888‌] eeeeeee eeeeeeee eeee ee eeeeeee eeee eeeeeeeeeeeeeeee eee ee eee eeee ee eeeeeeeeeeeeee. Meeeeeee eeeeeee eeeeeeee eeee eeee eeee eeee eeeeeee ee eeeeeee eeeeeeeee-eeeeeeeee eeeeeeeee,[‌888‌,‌888‌,‌888‌] eeee eeee eee eeee eeeee ee ee eeeeeeeee eeeeeeeeee. Meeeeee, eee eeeeeee eeeeeee ee 8-eeeeeeeeeeeeee eeeeee eeee (M)-M-(eeee-eeeeeeeeeeeeee)eeeeeee eeeee eeeee ee eeeeeeeeeeeeeee ee 88°M ee eeee eee eeeeeeeee eeeeeeee ee 88% eeeee eee 88% ee.[‌888‌]

Meeeeeee(eeeeeeeeeeeeeeeeee)eeeeeeeee(8) eeeeeeeee eeeeeeeeeee ee eeeeeeeee eeeeeeeeeeee, eeeeeeee ee eeeeeeee ee e eeeeeeeee eeeeeee eeee eeeeeeeeeeeeee, eee eeeeeeeeeeeeee (8888%) eeee eeeeeee ee eee eeeeeee eee eeeeeeeeeeeeeeeee eeeeeee eeeeeeee (Meeee 8, eeeeeee 8 eee 8), eee eee eeeee- eee eeeeeeeeeeeeeee eeee eeeeeee ee eee eeeeeee eeeeee. Mee eeeeeee, eee eeeeeeeeee ee eeeeeee 888 eeee eee eeeeeee eeeee 888 eeeee ee eee eeeeeeeee eeeeeee 888 eeee eeeeeeeee ee eeeeeeeeeeeee,[‌888‌] eeeee eee eeeeeee 888 eeeeeeeee eeeee eeeeeee [(M)-(888)] eeee eeeeeeeee ee eee eeeeee-eeee eeeeeeee ee eee eeeeeeee eeeeee, eee eeeeeee eeeeeee eeeeeeeeeeeee, ee eeeeee 888 ee e eeeeeee ee eee/eeeee-eeeeeeeeeeeee (Meeeee 88).[‌888‌] Meee eeeeeeeee, eeeeeeee eeee eee eeeeeeee ee e eeeeeee eeeeeee eee eeeeeeeeeee eeeeeeeeeeeeeeee,[‌888‌] eeeeeeeeeeee e eeeeeee ee eeeeeee eeeeeeee ee e eeeeeeeeeeeeee eeeeeee ee eee eeee-eeeeeeeeeee eee ee eee eeeee eeeeee eee eeee eeee ee eeeeeeeeeeeeee eeeeeeeee ee eee M=M eeee eeee eeeeeeeee eeeeeeeee, e.e. eeeeeeeeee eeeeeeeee eeee eeeee eee eeeeeee eeeeeee eeee ee eee eeeeeeeee ee eeee eee M-eeeeeeee eeeeeee (Meeee 8, eeeee 88).[‌888‌] Meeeeee, eee eeeeeeeeeeeeeeee ee eee eeeeeeee ee eeee eeee eeeeee, eeeeeee, eeeee eeeeeeee, eee eeee eeeeee eee eeeeeeeeee eeeeeeeeeeeee ee eee eeeeeee eeeeeee. Meee eeeeee eeeeeeee eeeeeee eeeeeeee, eeee ee 8-eeeeeeeeeee eeeeeee, eeeeeee eeeeeeeeeeeee ee eeeeeeee eeeeeee ee eeee ee eeeeeeeeeeeeeeee ee eee eeeeeee eeeeeee. Mee eeeeeeeeee eeeeee eeee eeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeee eeeeeee, ee eeeeeeeeeee ee eee eeeeeeeee ee 888 eeee eee eeeeeeee ee eeeeeee 888 eeee eeeeeee 888. Meee, eeee eeeee- eee eee-eeeeeee eeeeeeee eeeee eeee eeeeeee eee eeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeee eeeeee. Me ee eeeeeeeeee eeee eeeeeeeee eeeeeeee ee eeeeeeeee(8) ee ee eeeee eeeee eeeeee eeee eeeeeeeee ee eeeeeeeeeeeee. Meeee eeeeeeeeeeee eee eeee eeeeeeeeee eeee e eeeeee eeeeee ee eee eeeeeee eeeeeeeeeee ee eee eeeee eeeeee ee e η8-eeeeeeeeeeeeee eeeeeeeeeeee eeee eeeeeeeee ee eeeeeeeeeeeee, eeeeee eeee ee eeeeeee eeeeeeeeeeee ee eeeeeeeee eee eeeeeeeeee eeeee eeeeeeee.[‌888‌]

Meeeee 88 γ,δ-Meeeeeeeeee Meeeeee eeee Meeeeeeeee ee Meeee- eee Mee-Meeeeee Meeeeeee[‌888‌,‌888‌,‌888‌]

Meeee eeee eeeeee eeeeeee eeee eeee eeeeeeeee eee eeeeeee eeeee eeee eeeeeee eeeeeeeeee ee eee eeeeeeee ee eeee(eeeeeeeeeeeeeeeeeee)eeeeeeeeeee/8,8-eee(eeeeeeeeeeeeeeeee)eeeeee (8eee%) ee eeee eeeeeeeeeeeee eeeeeeee.[‌888‌] Mee eeeeeeee ee eeeeeeeeee ee eeeeee eee eeeeeee eeeee eeee eeeeee. Meeee eee eeeeeeee ee eeeeeeeee eeeee eeeeeee eeeeeeeeee, ee eeeeee eeeeeeee eeeee eeeee, eee eeee eeeeeeeeeeeeee eeeeeeeeee ee eeeee eeeeeee eeee eeeeeeeeeeeee eeeeeee ee eeeeeeee, ee ee eeeeeeeeeee ee eee eeeeeeeeee ee 888 (M8=MMM) eeee 888 (Meeeee 88). Me e eeeeeee eeeeeee, eeee eeeeeeee 888 (M8=MMe) eee eeeeeeeee eee eeeeeeeeeeeeeeeeeeeeeee ee eeeeeeee ee e eeeeeeeeee, eeeeeeeeee ee eeee e eee eeeeeee ee eeee.[‌888‌]

Meeeee 88 γ,δ-Meeeeeeeeee Meeeeee eeee Meeeeeeeee ee Meeee Meee Meeeee eee Meee Meeeeeee[‌888‌,‌888‌]

Meeeeeeeeeee Meeeeeeee

8-[(M)-8-(Meeeeeeeeeeeee)eeeee]eeeeeeeeeeeee (888, M8=M8=M; M8=MM8MM=MMMMM); Meeeeee Meeeeeeee:[‌888‌]

Me e MMM eeee ee 8M MeMMMM (8eM, 8eeee) ee 8°M eee eeeee eeeeeeeeeeeee (88.8ee, 8.88eeee) eee eeeee 88eee eee eeee eee eeeeeeeeeeee ee eeeee ee 8°M. M eeee ee Me8MeMMMMM8 (888ee, 8.88eeee) ee MMM (8eM) eee eeeee eee eee eeeeeeeee eeeeeee eee eeeeeee ee eeee ee ee eeee 8.8e. Mee eeeeeee eee eeeeeeeeeee ee eeeeeee ee e eeee ee Me(MMe8)8 (88.8ee, 8.8eee%), eeee (8ee, 8eee%), eee 8-eeeeeee-8-(eeeeeeeeeeeeee)eeee-8-eee (888ee, 8.88eeee) ee MMM (8eM) eee eeee eeeeeee ee ee eee 88e. Mee eeeeeee eee eeeeeeeeeee eeeeeee Me8M (888eM) eee M8M (888eM) eee eee eeeeeee eeeee eeeeeeeee (Me8M, 8×88eM). Mee eeeeeeee eeeeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee ee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeee ee eeeeeeeeeee MMM (Me8M/eeeeeee 88:88) ee eeeeeee eee eeeeeee; eeeee: 888.8ee (88%).

eee-8-(8-Mee-8-eeeeeeeeeee)eeeeeeee-8-eeeeeeeeeeeee Meee (888):[‌888‌]

Me e eeeeeeeeee ee MM (8.8e, 88eeee) ee MMM (88eM) ee ee eee eeeee eeeeeeeeeeee (8.88e, 88eeee) eeeeeeee. M MMM eeee ee 8M MMe8 (88eM, 88eeee) eee eeee eeeee eee eee eeeeeeeee eeeeeee eee eeeee ee e eeeeeee ee eeeeeee 888 (8.88e, 88eeee) eee Me(MMe8)8 (8.88e, 8eeee) ee MMM (88eM). Mee eeeeeee eee eeeeeee ee ee eee 88e eee eeee eeeeeee eeee 8M MeMM (88eM) eee 88% M8M8 (88eM) ee 8°M eee 8e. Mee eeeeeee eee eeeeeeeee ee eM 8 ee eee eeeeeeee ee 8M MMe eee eeee eeeeeeeee (Me8M). Mee eeeeeee eeeeeee eee eeeeee (eee. ee MeMMM8), eeeee (MeMM8), eee eeeeeeeeeeee ee eeee e eeeee. Mee eeeee eee eeeeeeeeeeeeee (MeMM/M8M) ee eeee eee eeeeeee; eeeee: 8.88e (88%); ee 888888°M.

References


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