Highly diastereo- and branched-selective rearrangement of substituted -alloc--allyl ynamides

An auto-tandem catalytic, branched-selective rearrangement of substituted N -alloc- N -allyl ynamides was developed. This reaction provides ready access to complex quaternary nitrile products with vinylogous stereocentres in excellent diastereoselectivity, including contiguous all-carbon quaternary...

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Published inChemical communications (Cambridge, England) Vol. 58; no. 84; pp. 11855 - 11858
Main Authors Jackson, Oliver D, Stankevich, Ksenia S, Cook, Matthew J
Format Journal Article
Published 20.10.2022
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Summary:An auto-tandem catalytic, branched-selective rearrangement of substituted N -alloc- N -allyl ynamides was developed. This reaction provides ready access to complex quaternary nitrile products with vinylogous stereocentres in excellent diastereoselectivity, including contiguous all-carbon quaternary centres. The stereochemical outcome is determined via a Pd(0) catalysed dipolar ketenimine aza-Claisen rearrangement and computational studies exemplify the key role ligand geometry plays. The use of a single palladium catalyst to perform two mechanistically distinct allylic rearrangements in excellent diastereoselectivity is described.
Bibliography:https://doi.org/10.1039/d2cc03399b
Electronic supplementary information (ESI) available. See DOI
ISSN:1359-7345
1364-548X
DOI:10.1039/d2cc03399b