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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Pd-Catalyzed Rearrangement of N -Alloc- N -allyl Ynamides via Auto-Tandem Catalysis: Evidence for Reversible C–N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement
- Award ID(s):
- 1800487
- PAR ID:
- 10297245
- Date Published:
- Journal Name:
- Organic Letters
- Volume:
- 23
- Issue:
- 2
- ISSN:
- 1523-7060
- Page Range / eLocation ID:
- 559 to 564
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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