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3.1.1.1.3.1.3 Reaction with Arenecarboxylates

DOI: 10.1055/sos-SD-209-00042

Zhang, M.; Su, W.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20133109.

Given that arenecarboxylates are more easily accessible than arenecarboxylic anhydrides it is unsurprising that they have also been investigated for the decarbonylative Mizoroki–Heck reaction with alkenes.[‌9‌] The screening of various aryl arenecarboxylates has revealed that substrates with an aryl group derived from an electron-deficient phenol can undergo palladium-catalyzed coupling, and that 4-nitrophenyl derivatives have optimal reactivity. The phenol formed from this reaction can be recycled to the starting ester by reaction with fresh arenecarboxylic acid catalyzed by scandium(III) trifluoromethanesulfonate (3 mol%), and only the flammable carbon monoxide and water are produced as waste. The coupling is typically conducted in 1-methylpyrrolidin-2-one at 160 °C in the presence of palladium(II) chloride (3 mol%) as the catalyst, isoquinoline (30 mol%) as the ligand, and lithium chloride (10 mol%) as an additive to afford aryl-substituted alkenes 13 and 14 as a mixture of regioisomers. The process has a wide substrate scope with respect to both esters and alkenes, and esters that contain halo, oxo, cyano, formyl, nitro, or protected amino groups all undergo smooth reaction in good yields (Scheme 7).

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M8 M8 Meeee (88/88) Meeeee (%) Mee
Me Me 88:8 – (88) [‌8‌]
8-MeMM8M8 Me 8:8 88 (88) [‌8‌]
8-MMM8M8 Me 88:8 88 (88) [‌8‌]
8-MeM8M8 Me 88:8 88 (88) [‌8‌]
8-MM8M8 Me 88:8 88 (88) [‌8‌]
8-Mee Me 8:8 88 (88) [‌8‌]
8-M8MM8M8 Me 88:8 88 (88) [‌8‌]
8-eeeeeeee Me 88:8 88 (88) [‌8‌]
8-MMMM8M8 Me 88:8 88 (88) [‌8‌]
8-M8MM8M8 Me 88:8 88 (88) [‌8‌]
8-MeM8M8 Me 88:8 88 (88) [‌8‌]
8-eMeM8MM8M8 Me 88:8 88 (88) [‌8‌]
8-MeMM8M8 Me 88:8 88 (88) [‌8‌]
8-eeeeeee Me 88:8 88 (88) [‌8‌]
8-eeeeeee Me 88:8 88 (88) [‌8‌]
(M)-MMMMMe Me 88:8 88 (88) [‌8‌]
8-MMM8M8 MM8Me 88:8 88 (88) [‌8‌]
8-MMM8M8 MM 8:8 88 (88) [‌8‌]
8-MMM8M8 M 88 (88) [‌8‌]
8-MMM8M8 8:8 88 (88) [‌8‌]

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M8 M8 Meeeee (88/88) Meeeee (%) Mee
Me MM8Me >88:8 88 [‌88‌]
Me Me 88:8 88 [‌88‌]
Me Me 88:8 88e [‌88‌]
8-eeeeeeee Me 8:8 88 [‌88‌]
8-MMMM8M8 Me 88:8 88 [‌88‌]
8-MMM8M8 Me 88:8 88 [‌88‌]
8-MeM8M8 Me 88:8 88 [‌88‌]
8-eeeeeee Me 88:8 88 [‌88‌]
8-MM8M8 Me 88:8 88 [‌88‌]
MMMMMe Me 8:8 88 [‌88‌]
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8-MeM8M8 Me 8:8 88 [‌88‌]
8-M8MM8M8 Me 8:8 88 [‌88‌]
8-Mee Me 88:8 88 [‌88‌]
8-M8MM8M8 Me 88:8 88 [‌88‌]
Me 8:8 88 [‌88‌]

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Meeee (M)-8-Meeeeeeeeeeeeeee (88, M8 = Me; M8 = MM8Me); Meeeeee Meeeeeeee:[‌88‌]

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References


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