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. 2015 Aug 18;51(64):12771-4.
doi: 10.1039/c5cc05312a.

Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: efficient access to α-alkyl vinylarenes

Changwu Zheng  1 , Shannon S Stahl
Affiliations

Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: efficient access to α-alkyl vinylarenes

Changwu Zheng et al. Chem Commun (Camb). .

Abstract

Branched-selective oxidative Heck coupling reactions have been developed between arylboronic acids and electronically unbiased terminal alkenes. The reactions exhibit high catalyst-controlled regioselectivity favoring the less common branched isomer. The reactions employ a catalyst composed of Pd(TFA)2/dmphen (TFA = trifluoroacetate, dmphen = 2,9-dimethyl-1,10-phenanthroline) and proceed efficiently at 45-60 °C under 1 atm of O2 without requiring other additives. A broad array of functional groups, including aryl halide, allyl silane and carboxylic acids are tolerated.

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Figures

Scheme 1
Scheme 1
Regioselectivity in Pd-catalyzed Heck coupling reactions.
Scheme 2
Scheme 2
Branched-selective aerobic oxidative Heck reactions with electronically unbiased alkenes
Scheme 3
Scheme 3
Preliminary ligand screening showing the influence of ligands on regioselectivity
Scheme 4
Scheme 4
Cationic versus neutral, five-coordinate pathways.
Scheme 5
Scheme 5
Transition state structures showing the steric contributions to branched vs. linear product formation.
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