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DOI: 10.1055/sos-SD-209-00042

Zhang, M.; Su, W.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20133107.

To avoid forming a stoichiometric amount of salt waste in Mizoroki–Heck reactions, a palladium-catalyzed decarbonylative coupling of arenecarboxylic anhydrides with alkenes has been developed. This procedure, which represents the first example of a base-free reaction,[‌7‌] is carried out in 1-methylpyrrolidin-2-one in the presence of palladium(II) chloride (0.25 mol%) as the catalyst. A catalytic amount of sodium bromide (1 mol%) is found to significantly improve the efficiency of the reaction, which, in addition to the desired alkenes 10 and 11, produces only carbon monoxide and a carboxylic acid as byproducts. In principle, the former can be easily burnt to give nontoxic carbon dioxide and the latter can be recycled into its corresponding anhydride. Furthermore, the method is applicable to a variety of alkenes under similar conditions at temperatures ranging from 140 to 190 °C (Scheme 5). Alkenes bearing electron-withdrawing groups generally afford β-arylated products in good yields, and both terminal and internal alkyl-substituted alkenes can serve as the substrate, giving a mixture of isomeric alkenes favoring the E-form.

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Meeeeeeeeee 8

Me8 M8 M8 M8 Meee (e) Meee (°M) Meeeee (%) Mee
Me (MM8)8 M 8 888 88 [‌8‌]
Me M MM8Me M 8.8 888 88 [‌8‌]
Me M (MM8)8Me M 8.8 888 88 [‌8‌]
Me M Me M 8 888 88 [‌8‌]
Me M MM8Me Me 8.8 888 88 [‌8‌]
8-MeMM8M8 M MM8Me M 8 888 88 [‌8‌]
8-eeeee M MM8Me M 8.8 888 88 [‌8‌]

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Meeeeeeeeee 8M

M8 M8 M8 Meee (°M) Meeee (88M/88M) Meeeee (%) Mee
M MM M 888 88:88 88 [‌8‌]
MM8Me MM8Me M 888 8:8 88 [‌8‌]

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Meeeeeeeeee 8

Me8 M8 Meeeeeeeeee Meeeee Meeeee (%) Mee
Me Me 88:8 88 [‌8‌]
8-MeMM8M8 Me 88:8 88 [‌8‌]
8-eeeeeeee Me 88:8 88 [‌8‌]
8-Mee Me 88:8 88 [‌8‌]
8-MeM8M8 Me 88:8 88 [‌8‌]
8-eeeeeee Me 88:8 88 [‌8‌]
8-MM8M8 Me 88:8 88 [‌8‌]
8,8,8-(MeM)8M8M8 Me 88:8 88 [‌8‌]
8-MeMM8M8 Me 88:8 88 [‌8‌]
8-eeeee Me 88:8 88 [‌8‌]
8-eeeee Me 88:8 88 [‌8‌]
8-eeeeeee Me 88:8 88 [‌8‌]
Me MM8e-Me 88:8 88 [‌8‌]
Me 8:8 88 [‌8‌]

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Meeeeee (M/M)-8-Meeeeeeee-8-eee-8,8-eeeeee (88M/88M, M8 = M8 = MM8Me; M8 = M); Meeeeee Meeeeeeee:[‌8‌]

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(M)-Meeeeeee (88, Me8 = M8 = Me); Meeeeee Meeeeeeee:[‌8‌]

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