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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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Meeeeeeeeee 8

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

Meeeeeeeeee 8

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]
8-MeMM8M8 Me 8:8 88 [‌88‌]
8-MeMM8M8 Me 8:8 88 [‌88‌]
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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8-Meeeeeeeeee 8-Meeeeeeeeee 88 eee 8-Meeeeeeeeee 8-Meeeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

M 88-eM eeeeeeee eeeeee eee eeeeeee eeee eee 8-eeeeeeeeeee eeeeeeeeeeeeeeee (8.8 eeee), MeMe8 (8.8 ee, 8.88 eeee), MeMe (8.8 ee, 8.8 eeee), eeeeeeeeeeee (88 ee, 8.8 eeee), eee MMM (8 eM). Mee eeeeee (8.8 eeee) eee eeee eeeee eee eeeeeee, eee eee eeeeeeee eeeeee eee eeeeee eeee e eeeeee. Mee eeeeeeeee eeeeeee eee eeeeeeee ee eeeeeeee eeeee eeeeeee eee eeee eee eeee eeeeee eeeeee ee 888 °M. Mee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MM eee, eeee eee eeeeeeee eee eeeeeeee (eeeeeee eeeee 8 e), eee eeeeeee eee eeeee ee ee eeeeeee eee eeeeee eeeeeeeeeeee eeee M8M, 8.8 M MMe, eee eee. ee MeMMM8. Mee eeeeeee eeeee eee eeeee (MeMM8) eee eeeeeeee, eee eee eeeeeeee eeeeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eeeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeee 8:8 ee 88:8) ee eeee eee eeeeeeee eeeeeeee eee 8,8-eeeeeeeeeeeee eeeeeeeeeee.

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

M 88-eM eeeee eee eeeeeee eeee MeMe8 (8.88 ee, 8.88 eeee), MM(MM8)8MMe8+Me (8.88 ee, 8.88 eeee), eee Meeeee (888 ee), eeeeee ee 888 °M eeeee eeeeee eee 88 eee, eee eeee eeeeeee eeee eeeee. Meeeeeeeeee eeeeeeee (888 ee, 8.8 eeee), eeeee eeeeeeee (888 µM, 8.8 eeee), eee MMM (8.88 eM) eeee eeeeeeeeeeee eeeee ee eeeeeee, eee eee eeeeeeeee eeeeeee eee eeeeeee eee 88 e ee 888 °M. Mee Me(8)/Meeeee eeeee eee eeeeeeeee ee eeeeeeeeee eee eee eeeeeeeee eeee eeeeeee eeeee eeee eeeeee. Mee eeeeeee eeeeeeee eee eeeeeeeeeeee eeeeeeeee ee eeee eee eeee eeeeeee ee e eeeeeeeee eeeeee; eeeee: 888 ee (88%); eeeee (88/88) >88:8.

References


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