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1.2.4.3.1 Addition of Water to Terminal Alkenes To Form Ketones; the Wacker Oxidation

DOI: 10.1055/sos-SD-001-00238

Takacs, J. M.; Vayalakkada, S.Science of Synthesis, (20011323.

The palladium(II)-catalyzed reaction of ethene with water to form acetaldehyde (the Wacker oxidation) is one of the most important industrial uses of palladium catalysis.[‌11‌‌14‌] While the precise mechanism for the reaction remains the subject of investigation,[‌15‌‌22‌] a popular mechanistic model is illustrated in Scheme 6. The model illustrates the requisite components for a successful reaction. A palladium(II) salt complexes the alkene (e.g., 21) and activates it towards addition of water. β-Hydride elimination affords the enol, which tautomerizes to the ketone 22. Reductive elimination affords HCl and Pd(0). The reaction proceeds to completion with a stoichiometric amount of the palladium(II) salt, but the addition of an oxidizing agent, to reoxidize palladium(0) to palladium(II), permits the use of catalytic palladium.

Meeeee 8 M Meeeee Meeeeeeeeee Meeee eee eee Meeeee Meeeeeeee ee Meeeee[‌88‌]

Mee eeeeeeee eee eeee eeeeeeee ee eeeeeeee eeeeeee. Mee eeeeeee eeeeeeee eeeeeeeeee eeeeeeee eee eeee eeeeeeeee eee eeeeeeeee eee eee eeee eeeeee ee eeeeeeeee ee e eeeeee.[‌88‌] Meeee eee eeee eeeeeee eeeeeeeee eeeeeeee eee eeeee eeee eeeeee eeeeeeeee eeeeeeeee(MM) eeeeeeee ee eee eeeeeeeee(MM) eeee, eeeeeee eeeeeeeeeeeeeeeee ee 8-eeeeeeeeeeeeeeee-8-eee[‌88‌,‌88‌] ee eee eeeeeeee eeeeeee, eee eeeeeeeee eeeeee(M) eeeeeeee eeeee ee eeeeee eeeeeeeeee ee eeee eeeee eeeeeeeeeeeeee eeeeeeeeeeee ee eee eeeeeeeee eeeee. Mee eeeeeeeeee eeee eeeee eeeeeeeeee, eeee eeeeeeeee ee eeeeeeee ee eeeeeeeeee eee eeeeeeee,[‌88‌] eee eeeeeeee eeeeeeeeee eeeee 88eee% eeeeeeeee(MM) eeeeeee eee 8.8 eeeeeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeeee/eeeeeee 8.8M eeeeeeeeee eeee (8:8) eee eeeeeeeeeeee eeeeeeee ee eeeee eeeee eeeeeeeee(MM) eeeeeeee eeeee ee eeeeee eeeeeeeeee eeeee.[‌88‌‌88‌] Me eee eeeeeeeeee eeeee eeeee eeeeeeeee eee eeeee eeeeee ee eee. Me eee eeee eeeee eeeeee ee eeeeeeee ee eee eeeeeeeee, eee eeeeeeee eeeeeeeee eeeeeeee eeee ee eeeeee eeeeeee eeeee eee eeeeeee ee eeeeee eeeeeeee eeeeeee, ee eeeeee eeeeeee eeeeeee eee eeeeeeee eeeeeee. Mee eeeeeeeeee eeeeeeee ee ee eeeeeeeee, eeeeeeeee, ee eeeeeeee ee eeeee eeeeeeeee eeee eeeee: eee eeeeeeeeeee eee eee ee eee eeeeeeeee eeeeeeeee,[‌88‌‌88‌] eeeeeee-eeeee eeeeeeeee,[‌88‌‌88‌] eeeeeeeeeeeee eeeeeeeee,[‌88‌‌88‌] eeeee-eeeeeeee eeeeeeeeee,[‌88‌,‌88‌] eeeeeeeeeeee eeeeeeeeee,[‌88‌] eeeeeeeeeeeeeee eeeeeeeee eeeeeeeeee,[‌88‌,‌88‌] eee eeeee eeeeeeeeeee eeeeeee.[‌88‌‌88‌]

Me eeee eeeee, eeeeeeee eeeeeee eeeeee eeeeee eeeeeee (eeeeeeeeee eee eeeee eeee eeeee). Mee eeeeeee, eee-8-eee (88) eeeeeee eeeee-8-eee (88) (Meeeee 8).[‌88‌,‌88‌,‌88‌] Mee eeeeeeee eeeeeeeeee eee eeee eee eeee eeeeee eeeeeeeeee eeeeee eee eeeeeeeee. Meeeeeeeee eeeeeeeeeeee ee eee eeeeee eeee eeee ee eeee eee eeee ee eeeeeeee eeeeeeeeeeeee, eee eeeee eeeeeee eeeeeeee eeeeeee eee ee eeeeeeee ee eeeeeeeeee (eeee eeeee), ee ee eeeee eeeeeeee ee eeeeeeeeeee eeeeeee ee eeeeeeeeee eeeeeeee eeeeee ee eeeee eeeeeeee, e.e. eee eeeeeeeee ee eeeeeeeeee 88 ee eeeee-8-eeee 88.[‌88‌‌88‌]

Meeeee 8 Mee Meeeeeeee-Meeeeeeee Meeeeeeee ee Mee-8-eee ee Meeee-8-eee eee Meeeeee Meeeeeee[‌88‌,‌88‌,‌88‌‌88‌]

Meeeeeeeeee 8

Meeeeeeeee Meeee (%) ee 88 Mee
MeMe8 (8.8 eeeee), MeMe, M8 (8 eee), MMM/M8M (8:8) 88 [‌88‌]
MeMe8 (8.8 eeeee), eeeee-8,8-eeeeeee, MMM/M8M (8:8) 88 [‌88‌]
Me(MMe)8 (8.88 eeeee), eeeee-8,8-eeeeeee, MMeM8, MeMM/M8M (8:8) 88 [‌88‌]

Me eeeeeeeee, eeeeeeeeee eeeeeeeeeeee ee eee eeeeee eeee eeee ee eeee eee eeee ee eeeeeeee eeeeeeeeeeeee. Meee eeeeeee eee eeee eeeeeeeee ee eeee ee eee eeeeeeeeeeee ee eeee eeeeeeee ee eeeee eeeeeeeee.[‌88‌] Mee eeeeeee, eee eeeeeeeeee ee eeeeeeeeeee-eeeeeeeeeee 8-eeeeeeeeeeeeeeeeee 88 [eeeeeee eeee (M)-eeeeeee] eeee eee 8,8-eeeeeeeeee eeeeeeee 88 eee eeeeee eeee eee eeeeeeeeeeeeee eeeeeeeee-8M-eeeee-8-eee 88 ee eeee ee eee eeeeeeeeee eeeeeeeee ee ()-8-eeeeeeeeeeeeee M.[‌88‌,‌88‌] Meee eeeeeeee eeeeeeeeee eee eeeeeeeee eeeeeeeee ee eee eeeeeeee eeeeee ee 88 ee eee eeeeeeee ee eee eeeeeeeee eeeee, ee eeee ee e eeeeee eee ee eeee eeeeeeeee-eeeeeeeee eeeeeeeee ee e eeeee ee eeeeeeeee 8,8-, 8,8-, ee 8,8-eeeeeeeeee eeeeeeeeeeeee, eeeeeee ee eeee ee ee eeeeeeeeee eeeeeeee (Meeeee 8).[‌88‌,‌88‌,‌88‌] Me eeeeee eeeee, eeee eeeeeeee eee eeee eeeeeeeee ee eee eeeeee ee eeeeeeeee eeeeee eeeeeeeeeee[‌88‌‌88‌] ee eeeeeeeee eeeeeeeeee ee eeeeeee eeeeeeee, eeee ee eeeeeeeeeeeee,[‌88‌] eeeeeee M,[‌88‌] eee eeeeeeeeeeeeeeeeee,[‌88‌] eee eeeeeeeeeeee,[‌88‌] eeeeeee eeeeeee eee eeeeee eeeeeeeeeeeee,[‌88‌] ee MM-eeee eeeee ee eeeee,[‌88‌] ee eeee ee ee eeeee eeeeeeeee eeeeeeeee eeee ee (+)-eeeeeeeeee M,[‌88‌] ()-eeeeeeeeeeee-M8,[‌88‌] eeeeeeee,[‌88‌] (+)-eeeeeeee eeee,[‌88‌] eee 88-eeeeeeeeeeeeeee eee eeeee eeeeeeee.[‌88‌‌88‌]

Meeeee 8 Mee Meeeeeeeeeeeee Meeeeeeee-Meeeeeeee Meeeeeeee ee ee Meeeeeeeeee-Meeeeeeeeee 8-Meeeeeeeeeeeeeeeee ee e 8,8-Meeeeeeeee Meeeeeee[‌88‌,‌88‌]

Meeeee eeeeeeeee eeeee eee eeeeeeee eeeeee ee eeeeeeee ee eeee eee eeee ee eeeeeeeee-eeeeeeeee eeeeeeeee.[‌88‌] Meeee eeee ee e eeeeeeeeee eeeeeeeeeee, eee eeeeee ee eee eeeeeeee eeeeeeeee eeee eeeeee eeeeeee eeeee ee eeeeeee. Meeeeee eeeeee eeeeeeee eeeeeeeeee eeeee eeeee eeeeeeeeee eeee eeeeeeeeee (eeeee ee ee) eee eeee eeeeeee eeeeeeeee eeeee (88e ee eeee). Mee eeeeeee, 8-eeeeeeeee-8-ee-8-ee (88) eeeeeeeee eeeeeeeee eeeeeeeee-eeeeeeeee eeeeeeeee ee 8-eeeeeee-8-eeeeeeeeeee-8-eee (88) (Meeeee 8).[‌88‌] Meeeeeeee, eee eeeeeeee eeeeeeee eeeeee 88 eeeeeeeee eeeeeeeee-eeeeeeeee eeeeeeeee eeeee eeeeeeee eeeeeeeeee eeee eee eeeeee ee 88eeeee ee eeeeeee eeeeeeeeeee ee eeee eee 8,8-eeeeeeeeee eeeeeeee 88 ee 88% eeeee.[‌88‌] Meeeeeeeeee ee 88 ee 88 eeee eee eeeee eee eee eeeeeeeee ee eeeeeeeee eeeeeee eee eeeeeeeeeeeeeeee eeeeeee. Meeee eeeeeeeee eeeee eeeeeeeee eee eee ee eee Meeeee eeeeeeeee ee eeeeeeee 8,8-eeeeeeeeee eeeeeeeeeeeee. Meee, eee eeeeeeeee eee eee Meeeee eeeeeeeee, eeeeeeeeeee eeeeeeee 88, ee eeeeeeeeeee eee e Meeeeee eeeeeeeeeeeee. Me eeeeee ee eeeee eeee eee eee ee e Meee ee ee eee-Meee eeeeeeeeeeeee ee eee ee e eeeeeeeeee Meeeee eeeeeeeee ee e eeeeee eeeeeeeee eeeeeeee.[‌88‌]

Meeeee 8 Meeeeeeeee Meeeeeeee-Meeeeeeee Meeeeeeee ee Meeeeeee Meeeeeee Meeeeee[‌88‌,‌88‌]

Me eeeee ee eee eeeeeeeee eeeeeee, eeee eeeeeeeeeee ee eeeeeeeeeeee eeeeeee ee eee eeeee eeeeeeeee ee eeeeeee eeeeeeeee.[‌88‌] Mee eeeeeeeee ee eeeeeeeeee[‌88‌,‌88‌] eeeeeeee eee eeeeee eeeeeeeeee ee eee eeeeeeeeeee eeeeeeeeee 88 eeee eeeeee eeeeee 88 (Meeeee 88). Meeeeeeee eeeeeeeeeeeee ee eee eeeeee-eeeeeee α-eeeeeeeeeeee ee eeeeeeeeee eee e eeeeeee eeeee eee eeeeeeee eeeeeeeeee.

Meeeee 88 Meeeeeeee-Meeeeeeee Meeeeeeee Meeeeeee eeeeeee Meeeeeeeeeeee α ee eee Meeee Meeeee Meeeeeee (Meee ee eee Meeeeeeeee Meeeeeeee ee Meeeeeeeee)[‌88‌,‌88‌]

Meeeeee eeeeee eeeeeeeee eee ee eeee eeeeeeeee-eeeeeeeee eeeeeeeee ee ee eeeeeeeeeee eeee ee eeeeeeeeee eeeeeeeeee, ee eeeeee eee eeeeeeeeee ee ee eeeeeeeeee eeeee eeeeeeee ee eeeeeee ee eeeee eeeeee eeeeeee. Mee eeeeeee, 88 ee eeeeeeee eee eee eeeeeeeeee eeeeeeeeee ee (M)-8-(eeeeeeeee)-8-eeeeeeeeeeeeee eeeee eeeee(eeeeeeeeeeeeeeeeee)eeeeee.[‌88‌] Meeeeeeee-eeeeeeeee eeeeeeeee ee eeeeeeeeeee eeeee 88 eeeeeee β-eeeeeee eeeeee eeeeee eeeeeeeeee 88 (Meeeee 88), e eeeeeeee eeee ee eeee ee eee eeeeeeee ee eeeeeeeee M.[‌88‌] Meeeeeeee, (8M,8M)-8-[(M)-8,8-eeeeeee-8,8-eeeeeeee-8-ee]-8-eeeeeeeee-8-ee-8-ee, eeeeeeee eee eeeeeeeeee (M)-eeeeeeeeeeeeee ee M-eeeeeeeeeeeeee eeeeeeeeeee eeeee,[‌88‌] ee eeee eee eee eeeeeeeeeee ee 8,8-eeeee 88. Meeeeeeee-eeeeeeeee eeeeeeeee ee 88 eeeeeee β-eeeeee eeeeee eeeeee 88, e eeeeeee eeee ee ee eeeeeeee ee eeeeeeeeee M8.[‌88‌] Mee eeeeeeee eeeeeeee eeeeeeeeeeeeeeee (e.e., eee eeeeeeeeee eeeeeeeee ee eeeeeeeeee) eee eeeee, eeeeeee eeeeeeeeeeeee ee eee α eeeeee eeeeee. M eeeeeee eeeeeeee, eee eeeeeeeeee ee 88 eeee 88 eeee ee eee eeeeeeeee ee eeeeeeeeee M eee eeeeeeeeeee M, eeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeee ee eee eeeeeeeee-eeeeeeeee eeeeeeeee eee eee eeeeeeeee ee eeeeee eeeeeeeeeeeee (e.e., eeeeeeee, eeeeeeee eeeeee eeee, MMMMM eeeee).[‌88‌,‌88‌] Mee eeeee ee eeeee eeeeeeeeee eeeeeeeee eee eeeeeeeee ee eee eeeeeeee ee eeeeeeeee β-eeeeee eeeeeee eeeeee. Meeeeee eeeeeeeeee eee eeeeeeee ee eeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeee M,[‌88‌] eeeeeeeeeee eeee,[‌88‌] eee eee eeeeeeeee eeeeeeeeeeeeeeeeee,[‌88‌] eeeeeeeee,[‌88‌] eee eeeeeeee-e.[‌88‌]

Meeeee 88 Meeeeeeeee Meeeeeeeee Meeeeeee ee Meeeeeeee-Meeeeeeee Meeeeeeee ee ee Meeeeeeeee ee eee Meeeeeeeee Meeee ee e Meeeee Meeeee[‌88‌‌88‌]

Me eeeeeeee ee eeeee eeeeeeee, eee eeeeeeeee-eeeeeeeee eeeeeeeee ee e eeeeeeee eeeeee eee eeeee eeeeeeeeeee ee e eeeeee ee eeeee eeeeee eeeeeeeee eeeeeee, eeeeeeeee eeeee eeeeee eeeeeee eeeeeee,[‌88‌] eeeeeee eeeeeeeee,[‌88‌] eeeee'e eeeeeeeee,[‌88‌] eeeeeeeeeeeeeeee M,[‌88‌] (+)- eee ()-eeee-eeeeeeeeee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeee-8-eee (88) eeee Mee-8-eee (88) Meeee Meeeeeeee(MM) Meeeeeee, Meeeee(M) Meeeeeee eee Meeeee:[‌88‌]

Meeeeeeee eeee (Meeee; Meeeeeeee; Meeeee, Meeeeee Meeeeeeee), Meeeeeeee (8888), e8, eeee eeeeeeeeee eeee Meee Meeee & Meee, Mee.

M eeeeeee ee MeMe8 (8.88e, 8eeee) eee MeMe ee MMM (88eM) eee M8M (8eM) eee eeeeeee eeeee M8 (8 eee, M8 eeeeeee) eee 8e eeee eeeee eeee eee eeee eeee eeee eeeee ee eeeee. Meeee 8e, e eeee ee eee-8-eee (88; 8.8e, 88eeee) ee MMM (8eM) eee M8M (8eM) eee eeeee eeeeee (MMMMMMM: eeeeeeee) eeee eeeeeeee eeeeeeee eee eeeeeee ee ee eee eeee ee eeeeee. Mee eeee eeeeee eeeee (88eee), eeee eeeeee eeeeeeee ee eeeee. Meeee 88e, eee eeeeeee eee eeeeee eeee eeee 8M MMe. Meeeeeeeee eeeeee eeeeeeee ee eeeeeeeeeeee ee eeeeeee eeeeeeee eeeeeeee eeeee-8-eee ee e eeeeeeeee eee; eeeee: 8.8e (88%); ee 8888°M/8Meee.

Meeee-8-eee (88) eeee Mee-8-eee (88) Meeee Meeeeeeee(MM) Meeeeeee eee Meeee-8,8-eeeeeee:[‌88‌]

Me e eeeeeee eeeeeee ee MeMe8 (88ee, 8.8eeee) eee eeeee-8,8-eeeeeee (8.88e, 88eeee) ee MMM/M8M (8:8, 88eM) eee eeeeee eeeee eee-8-eee (88; 8.8e, 88eeee eeee 88eee). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 8e eeee eeeeee eeee eeee 8M MMe (888eM). Meeeeeeeee eeeeee eeeeeeee ee eeeeeeeeeeee ee eeeeeee eeeeeeee eeeeeeee eeeee-8-eee; eeeee: 8.8e (88%).

Meeee-8-eee (88) eeee Mee-8-eee (88) Meeee Meeeeeeee(MM) Meeeeee, Meeee-8,8-eeeeeee, eee Meeeeeeeee Meee ee Meeeeee Meeeeeeeeeee:[‌88‌]

Me(MMe)8 (88ee, 8.8eeee), eeeee-8,8-eeeeeee (888ee, 8eeee), eee MMeM8 (88% e/e, 8.8eM) eeee eeeeeeeee ee MeMM/M8M (88eM). Mee eeee eee eeeeeeeeeeee ee eeeeeee eeee eeeee eee ee eeeee 88eee eee eeeeeee eeeeeeeeee eeeee eee Me(MMe)8 eee eeeeeeeee. Mee eee-8-eee (88; 8.88e, 88eeee) eee eeee eeeee eee eee eeeeeee eeeeeee eee 88eee. Meeeeeeeee eeeeee eeeeeeee eeeee-8-eee; eeeee: 88% (MM eeeeeeee ee ee eeeeeeee eeeeeeee).

References


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