Divergent Catalysis: Catalytic Asymmetric [4+2] Cycloaddition of Palladium Enolates
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1.
California Institute of Technology
Abstract
An asymmetric decarboxylative [4+2] cycloaddition from a catalytically generated chiral Pd enolate was developed, forging four contiguous stereocenters in a single transformation. This was achieved through a strategy termed divergent catalysis, wherein departure from a known catalytic cycle enables novel reactivity of a targeted intermediate prior to re-entry into the original cycle. Mechanistic studies including quantum mechanics calculations, Eyring analysis, and KIE studies offer insight into the reaction mechanism.
Additional Information
© 2023 American Chemical Society. This publication is licensed under CC-BY 4.0. The NIH-NIGMS (R35GM145239), Heritage Medical Research Investigators Program, and Caltech are thanked for the support of our research program. The authors thank the Caltech High Performance Computing Center for support. The authors thank Dr. David VanderVelde (Caltech) for NMR expertise, Dr. Mona Shagholi (Caltech) for mass spectrometry assistance, and Dr. Scott Virgil (Caltech) for instrumentation and SFC assistance. P.C. and C.S.S. would like to thank the NSF GRFP for funding. W.A.G. thanks the NSF (CBET-2005250) for support. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. This manuscript is dedicated to the memory of Jiro Tsuji (1927–2022). Author Contributions. K.N.F. and A.Q.C. contributed equally. The authors declare no competing financial interest.
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Additional details
- Eprint ID
- 121759
- Resolver ID
- CaltechAUTHORS:20230607-310749000.5
- DOI
- 10.1021/jacs.3c02104
- PMCID
- PMC10388310
- R35GM145239
- NIH
- Heritage Medical Research Institute
- CBET-2005250
- NSF
- NSF Graduate Research Fellowship
- Created
-
2023-06-08Created from EPrint's datestamp field
- Updated
-
2023-06-08Created from EPrint's last_modified field
- Caltech groups
- Heritage Medical Research Institute, Resnick Sustainability Institute
- Other Numbering System Name
- WAG
- Other Numbering System Identifier
- 1569