Science of Synthesis

Landais, Y.; Vincent, J. M., Science of Synthesis, (2005) 26, 658.

Oxidative addition of alkyl and aryl halides to palladium(0) catalysts followed by carbonylation gives palladium–acyl complexes, which can then react in a number of ways to provide carbonyl compounds. Similarly, carbonylation of aryl halides/hexaalkyldistannane systems mediated by palladium(0) complexes affords symmetrical 1,2-diketones (‌Scheme 14‌).[‌34‌] The reaction is believed to proceed by oxidative addition of an aryl iodide to a palladium(0) complex in the presence of carbon monoxide thus generating an acylpalladium species Pd(COAr1)L2. This then undergoes transmetalation with hexaalkyldistannane to form an acyltrialkylstannane intermediate. Coupling between the latter species and the above acylpalladium Pd(COAr1)L2, followed by reductive elimination then produces the desired 1,2-diketone. As an illustration, carbonylation of 4-iodoanisole (‌53‌) under a carbon monoxide atmosphere in the presence of bis(η3-allyl)dichlorodipalladium complex gives the corresponding 1,2-diketone ‌54‌ in good yield together with a small amount of the corresponding ketone. Vinyl trifluoromethanesulfonates have been used instead of alkyl halides in a closely related palladium-catalyzed coupling reaction with (1-ethoxyvinyl)tri­methylstannane in the presence of carbon monoxide; this gives the divinyl ketone as its enol ether, which is readily hydrolyzed to the 1,2-diketone.[‌38‌] A three-component palladium-catalyzed synthesis of 1,2-diketones has been reported that involves a pentacarbonylchromate ‌55‌, a vinyl (or an aryl) iodide, and carbon monoxide. Several unsymmetrical 1,2-diketones are thus prepared in moderate to good yield; an example is shown in ‌Scheme 14‌ using 1-iodo-2-phenylethene as the vinyl iodide, giving the unsymmetrical 1,2-diketone ‌56‌ as the product.[‌39‌]

‌Meeeee 88‌ Meeeeeeee-Meeeeeee Meeeeeeeeeeee Meeeeeee ee Meee Meeeeee[‌88‌,‌88‌]

Me e eeeeeee eeeeeee, eeeeeeee eeeeeee, eeeeeeeee eeee eeeeeee eeeeeeeee eeeeeeee eeeeeeeeeeeeeeeeeeee (‌88‌) eeeee e eeeeee eeeeeeee eeeeeeeeee, eeee 8,8-eeeeeeeee (‌Meeeee 88‌).[‌88‌] Meeeeeee eeeeeeeeeeeeeeeeeeee (‌88‌) ee eeeeeee eeeeeeee ee eee eeee ee eeeeeeeee ee eeee(MMM) eeeeeeee ee eeeeeeeeeeeeeeeee eeeee e eeeeeeeeeee–eeeeee eeeeee. Me eeee eeeeee eeee eeeee eeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeee ee eeee eeeeeeeeeeee ‌88‌. Meeeeeee ee 8 eeeeeeeeeee ee eeeeee(M) eeeeeeee eeeeeee ee eee eeeeeeeee ee eee eeeeeee 8,8-eeeeeeeee ‌88‌ ee eeee eeeee. Meeeeeee eeee eeeeeeeeeee eeeeeee-eeeeeeeeeee 8,8-eeeeeeeee eeee eeee eeeeeeeeeee ee eeee eeeee, eeeeeeeeeeeee eee eeeeee eeeeeeeee ee eeeeee ee eeee ee ee eeeee eeeeeeee. Me ee eee eeeee eeeeeee eee eeeeee eeeeeeee eeeeeee ee ee eeeeeeeeee eeeeeeeeeeee, eeeeee eeeeeee eeeeeeeeeeeeeee ee eeee, eeeee eeee eeeeeeeeee ee eeee eee eeeeeeeeeee 8,8-eeeeeeee. Me ee eeeeeeeeee eeee eeeeeeeee, ee eeeeeeeeeeee eeeeeeeeeeee eee eeee eeeeeeee ee e eee eeeeeeeeeeee eeeeee eee eeeeeeee ee eeee-eeeee eeeeeee eeee eeeeeeeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeee.[‌88‌] Me eeee eeee, eee eeeeeeee eeeee eeeeeee eeeee eeeeeeee, e 8,8-eeeeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeeeee ee 8,8-Meeeeeeee eee Meeeeeeee ee Meeeeeeeeeee[‌88‌]

M eeeeeee eeeeeee eeeeeee eeeeee eeee eeeeeeee eeeeeeeeeeee eeeeeeeeee (‌Meeeee 88‌).[‌88‌] Meeeeeeeee ee eeeeeeeeeeeee ‌88‌ eeeee eeeeeeeeeeee, eeeeeeee ee eeeeeeeeeeeeeee eeee eeeeeeeeeeeeeeeee, eee eeeeeeee eeee ee eeeee eeeeee eeeeeeee, eeeee eeeeeeeeee, eee eeeeeeeeeeeee 8,8-eeeeeeeee ‌88‌ ee eeee eeeeee. Meeeee eee eeeeeeeeeee eeeeeeeeeee, eeee eeeeeeee eeeeeee eeeeee ee eeeeeeeeeeeee eeee- eee/ee eeeee-eeeeeeeeeee 8,8-eeeeeeeee, eeeeeee ee eeeeeeee ee eeeeeeeeeeeeee 8,8-eeeeeeeee eeee eeee eeeeeeeeeee. Me eeeeeeee eeee eeeee, eee eeeeeeee ee eeeeee ee eeeeeee eeeeeee ee eeeeeeeeeeeeeeeeeeeeeeee eeee ee ‌88‌ (‌Meeeee 88‌).

‌Meeeee 88‌ Meeeeeeeeee ee 8,8-Meeeeeeee ee Meeeeeee ee Meeeee Meeeeeeeeeee eeee Meeee Meeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

Me e eeeeeeeeee ee Me8Me(MM)8 (88 eeee) ee eeeee MMM (88 eM), eee eeeee eee eeeee eeeeeee (88 eeee) eee MM eee eeeeeee eeeeeee eee eeeeeee eee 88 eee ee 88°M. Mee MM eeeeeeeeee eee eeeeeeee ee eee M8 eee MeMe (88 eeee) eee eeeee eee eee eeeeeee eee eeeeeee ee 88°M eee 8.8 e. Mee eeeeeee eee eeeeee eeee M8M eeeeeeeeee MMM (88 eeee) ee eeeeeeeee eee eeee eeeeeeee. Mee eeeeeee eeeee eee eeeeeeee eee eee eeeeeee eeeee eeeeeeeee eeee MeMe eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeee (MeMM8) eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeee ee eeeeee eeeeeeeeeeeeee ee eeee 8,8-eeeeeeee ‌88‌; eeeee: 88–88%.

8-Meeeeeeeeeeee-8,8-eeeee (‌88‌, M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeee, eeeeeeeee, ee eeeeeeeeee ee eeeeeeeeeee eeeeeee eee eeee eee ee eeeee.

Me e eeee ee eeeeeeeeeeee eeeeeeee eeeeeeeeeeee (8.88 e, 88 eeee) ee MMM (88 eM) eee eeeee e eeee ee MeMe ee eeeeee (88 eeee) ee 8°M eee eee eeeeeee eee eeeeeee eee 88 eee ee eeee eeeeeeeeeee. Me(MM)8 (8.88 e, 88 eeee) eee eeeee eee eee eeeeeee eee eeeeeee ee ee eee 88 eee. MeM (8.88 e, 88 eeee) ee MMM (88 eM) eee eeee eeeeeeeeee. Meeee 8 e, eee eeeeeee eee eeeeeee eeeee eeeeee eee eee eeeeeee eeeeeeeeee eeee M8M. Mee eeeeeee eee eeeeeeeee eeee Me8M eee eee eeeeeeee eeeeeeee eeeee (Me8MM8). Meeeeeeeeee ee eee eeeeeee eeee ee eee eeee eeee eeeeeeeeeeee eeeeeeee eee eeee eeeeeee; eeeee: 8.88 e (88%).

References

Meeeeee Meeeeeeeeee

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