Enantioselective Michael Spirocyclization of Palladium Enolates
Creators
-
1.
California Institute of Technology
Abstract
We report an enantio- and diastereoselective Michael spirocyclization reaction of tetrasubstituted palladium enolates. This allows for the formation of adjacent all-carbon quaternary and tertiary stereocenters in good yield, dr, and ee. Various subsequent cyclization reactions enable access to a diverse range of tricyclic scaffolds. The mechanism of this trans-formation is evaluated via quantum mechanics calculations to elucidate the origins of stereoselectivity and the mechanism of catalyst turnover.
Copyright and License
The content is available under CC BY NC ND 4.0
Acknowledgement
The NIH-NIGMS (R35GM145239), Heritage Medical Research Investigators Program, and Caltech are thanked for the support of our research program. We also thank Dr. David VanderVelde (Caltech) for his NMR expertise, Dr. Mona Shahgoli, Dr. Scott C. Virgil, and Jay Barbor (Caltech) for their assistance with mass spectrometry and other instrumentation, Dr. Michael K. Takase (Caltech) for assistance and expertise with X-ray crystallography. The authors extend additional thanks to Dr. Alexander Q. Cusumano, Kevin J. Gonzalez, and Elliot F. Hicks for helpful discussions. C.S.S. and P.C. would like to thank the NSF GRFP for funding. W.A.G. thanks the NSF (CBET 2311117) 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. The authors thank the Caltech High Performance Computing Center for support.
Supplemental Material
Funding
- NIGMS R35GM145239
- NSF CBET 2311117
Data Availability
CCDC 2421482–2421483 contain the supplementary data for this paper. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033
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Additional details
Funding
- National Institute of General Medical Sciences
- R35GM145239
- Division of Chemical, Bioengineering, Environmental, and Transport Systems
- CBET 2311117
- National Science Foundation
- Graduate Research Fellowship Program -