Asymmetric synthesis of chiral cycloalkenone derivatives via palladium catalysis† †Electronic supplementary information (ESI) available: Detailed experimental procedures and copies of NMR spectra and HPLC chromatograms. See DOI: 10.1039/c3sc53250j Click here for additional data file.

نویسندگان

  • Barry M. Trost
  • James T. Masters
  • Jean-Philip Lumb
  • Dahlia Fateen
چکیده

The palladium-catalyzed oxidative desymmetrization of meso dibenzoates yields γ-benzoyloxy cycloalkenones in good yields and with excellent levels of enantioselectivity. These compounds serve as precursors to a broad range of substituted cycloalkenones, including well-established synthetic building blocks and elaborated cycloalkanone derivatives. The ability to prepare both enantiomers of the oxidative desymmetrization products enables a unified strategy toward stereochemically diverse epoxyquinoid natural products.

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منابع مشابه

Asymmetric synthesis of cyclopentanes bearing four contiguous stereocenters via an NHC-catalyzed Michael/Michael/esterification domino reaction† †Electronic supplementary information (ESI) available: Experimental procedures and characterization date (NMR, IR, MS, HPLC). CCDC 1437686. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5cc09581f Click here for additional data file. Click here for additional data file.

An NHC-catalyzed Michael/Michael/esterification domino reaction via homoenolate/enolate intermediates for the asymmetric synthesis of tetrasubstituted cyclopentanes bearing four contiguous stereocenters is described. A variety of α,β-unsaturated aldehydes and 2-nitroallylic acetates react well with good domino yields and high stereoselectivities.

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Reagent-controlled enantioselectivity switch for the asymmetric fluorination of β-ketocarbonyls by chiral primary amine catalysis† †Electronic supplementary information (ESI) available: Experimental details including characterization date, copies of 1H, 13C, and 19F NMR and HPLC traces. See DOI: 10.1039/c6sc03109a Click here for additional data file.

A reagent-controlled enantioselectivity switch was uncovered in the asymmetric a-fluorination of bketocarbonyls by a chiral primary amine catalyst. By a simple swap of fluorination reagents, both enantiomers of the quaternary fluorination adducts could be obtained with good yields and high enantioselectivity. Mechanistic studies disclosed dual H-bonding and electrostatic stereocontrolling modes...

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عنوان ژورنال:

دوره 5  شماره 

صفحات  -

تاریخ انتشار 2014