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Updated: Aug 26, 2025

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Highly diastereo- and branched-selective rearrangement of substituted N-alloc-N-allyl ynamides
Oliver D Jackson1, Ksenia S Stankevich1, Matthew J Cook1
1Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT 59717, USA. matthewcook@montana.edu.
Abstract:
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.
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