A general and highly selective chelate-controlled intermolecular oxidative Heck reaction.
A novel chelate-controlled intermolecular oxidative Heck reaction is reported that proceeds with a wide range of nonresonance stabilized alpha-olefin substrates and organoboron reagents to afford internal olefin products in good yields and outstanding regio- and E: Z stereoselectivities. Pd-H isomerization, common in many Heck reactions, is not observed under these mild, oxidative conditions. This is evidenced by outstanding E: Z selectivities (>20:1 in all cases examined), no erosion in optical purity for proximal stereogenic centers, and a tolerance for unprotected alcohols. Remarkably, a single metal/ligand combination, Pd/bis-sulfoxide complex 1, catalyzes this reaction over a broad range of coupling partners. Given the high selectivities and broad scope, we anticipate this intermolecular Heck reaction will find heightened use in complex molecule synthesis.
Delcamp
Jared H
JH
University of Illinois Urbana-Champaign, 600 S. Mathews, Urbana, Illinois 61801, USA.
Brucks
Alexandria P
AP
White
M Christina
MC
D000475:Alkenes / Q000737:chemistry*; D001672:Biocompatible Materials / Q000138:chemical synthesis*; D002384:Catalysis; D002614:Chelating Agents / Q000737:chemistry*; D002625:Chemistry, Organic / Q000379:methods*; D006859:Hydrogen / Q000737:chemistry; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D012451:Safrole / Q000031:analogs & derivatives / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D001672:Biocompatible Materials; D002614:Chelating Agents; D010165:Palladium; D006859:Hydrogen; D012451:Safrole; C005746:sulfoxide