2018
DOI: 10.1021/jacs.8b02751
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Formation of Chiral Allylic Ethers via an Enantioselective Palladium-Catalyzed Alkenylation of Acyclic Enol Ethers

Abstract: This report details a palladium-catalyzed process to access highly functionalized optically active allylic aryl ethers. A number of electron-deficient alkenyl triflates underwent enantio- and site-selective coupling with acyclic aryl enol ethers in the presence of a chiral palladium catalyst. This transform provides chiral allylic ether products in high yields and excellent enantiomeric ratios furnishing a unique disconnection to incorporate heteroatoms at a stereocenter. Finally, the applicability of the prod… Show more

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Cited by 50 publications
(24 citation statements)
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“…A Pd 0 precatalyst was required to initiate the oxidative addition of the alkenyl triflate . We explored various alkenyl triflates that have historically been successful in the acyclic systems . This includes the use of 6‐membered endocyclic alkenyl triflates to cleanly generate products 6 a (86%) and 6 b (67%).…”
Section: Methodsmentioning
confidence: 99%
“…A Pd 0 precatalyst was required to initiate the oxidative addition of the alkenyl triflate . We explored various alkenyl triflates that have historically been successful in the acyclic systems . This includes the use of 6‐membered endocyclic alkenyl triflates to cleanly generate products 6 a (86%) and 6 b (67%).…”
Section: Methodsmentioning
confidence: 99%
“…More recently our group has explored alkenes bearing various unique functional groups (Scheme ). As an example, coupling of indole triflate 4 and enol ether 24 provided aldehyde 23 . This reaction affords an enantioenriched secondary ether adjacent to the indole C2 position, a product not accessible using reported organocatalytic approaches.…”
Section: Methodsmentioning
confidence: 99%
“…As an example, coupling of indole triflate 4 and enol ether 24 provided aldehyde 23 . 14 This reaction affords an enantioenriched secondary ether adjacent to the indole C2 position, a product not accessible using reported organocatalytic approaches. Use of commercially-available cis -4-nonenal 25 afforded α,β-unsaturated aldehydes 26a - c in high yield and good enantioselectivity.…”
mentioning
confidence: 99%
“…Recently, we have reported an alternative approach to allylic ethers through the use of enantioselective, redox-relay Heck reaction of O-aryl enol ethers (B) and alkenyl triflates (Scheme 1A). [7] The redox-relay Heck reaction differs from the traditional Heck reaction in that the unsaturation of the olefin is relayed along the carbon chain toward a redox acceptor, such as an alcohol, resulting in oxidation and yielding a carbonyl product. [8] By using an enol ether, it was hypothesized that the oxygen of the alkene would significantly polarize it such that the migratory insertion would occur regioselectively, forming a bond between a cross coupling partner and the proximal alkenyl carbon with respect to the ether (See intermediate C, Scheme 1A).…”
Section: Introductionmentioning
confidence: 99%