Ir-Catalyzed Asymmetric Allylic Alkylation of Dialkyl Malo-nates Enabling the Construction of Enantioenriched All-Carbon Quaternary Centers
Abstract
An enantioselective iridium-catalyzed allylic alkylation of malonates with trisubstituted allylic electrophiles to form all-carbon quaternary stereocenters is reported. This cross-coupling reaction features unprecedented reactivity at ambient temperature, particularly for challenging fully alkyl-substituted allylic electrophiles, and enables the preparation of a wide range of enantio-enriched products in up to 93% yield and 97% ee. The products of this transformation can be readily converted to a number of valuable building blocks including vicinal quaternary stereodiads and β-quaternary acids. This method was also used to prepare an enantioenriched intermediate facilitating the asymmetric formal synthesis of the sporochnol family of natural products.
Additional Information
The content is available under CC BY NC 4.0 License. The authors would like to thank Dr. Mona Shagholi for mass spectrometry assistance and Dr. Scott Virgil for assistance with instrumentation. The NIH-NIGMS (R01GM080269) and Caltech are thanked for their support of our research program. E. F. H. and Z. P. S. would like to thank the NSF GRFP for funding. Author Contributions. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. The authors declare no conflict of interestAttached Files
Supplemental Material - experimental-section.pdf
Supplemental Material - spectra.pdf
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Additional details
- Eprint ID
- 113993
- Resolver ID
- CaltechAUTHORS:20220322-742009000
- R01GM080269
- NIH
- Caltech
- NSF Graduate Research Fellowship
- Created
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2022-03-23Created from EPrint's datestamp field
- Updated
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2023-03-24Created from EPrint's last_modified field