Cascade Grignard Addition: Propargyl Claisen Rearrangement for the Stereoselective Synthesis of α-Allene Quaternary Centers in Cyclohexanones
We report a new method for the enantio- and diastereoselective synthesis of α-allene quaternary centers in fully substituted cyclohexanones at the α-positions. This reaction involves asymmetric 1,2-carbonyl addition to 2-<i>O</i>-propargyl enones using a mixture of Grignard reagents and the PMP-H8-BINOL ligand. The resulting magnesium alkoxide chelate intermediate then activated the propargyl vinyl ether moiety, thereby triggering a cascade propargyl Claisen rearrangement in a diastereoselective manner. The synthetic applications of this method in the context of complex molecules are also demonstrated.
Authors
- Edward W. Mureka (ORCID: https://orcid.org/0000-0002-2834-0774)
- Frank Rolf Fronczek (ORCID: https://orcid.org/0000-0001-5544-2779)
- A. Muhammad Afdhal Saputra (ORCID: https://orcid.org/0000-0003-1330-214X)
- G.K. Tan (ORCID: https://orcid.org/0000-0002-9053-2611)
- Rendy Kartika (ORCID: https://orcid.org/0000-0002-2042-2812)
- Estefania Armendariz-Gonzalez
- Cale M. Locicero
- Andrew Watson
- Gabrielle L. Womble
Institutions
- Louisiana State University (US)
Publication Details
- Journal
- Organic Letters
- Published
- 2025-06-18
- DOI
- https://doi.org/10.1021/acs.orglett.5c02006
- Citations
- 1
- Primary Topic
- Catalytic Alkyne Reactions
- Type
- article
- Field-Weighted Citation Impact
- 0.94
Funders
- Louisiana State University
- National Institute of General Medical Sciences
- Division of Equity for Excellence in STEM