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The Cyanthiwigin Natural Product Core as a Complex Molecular Scaffold for Comparative Late-Stage C–H Functionalization Studies

Kim, Kelly E. and Adams, Ashley M. and Chiappini, Nicholas D. and Du Bois, J. and Stoltz, Brian M. (2018) The Cyanthiwigin Natural Product Core as a Complex Molecular Scaffold for Comparative Late-Stage C–H Functionalization Studies. Journal of Organic Chemistry, 83 (6). pp. 3023-3033. ISSN 0022-3263. https://resolver.caltech.edu/CaltechAUTHORS:20180109-144403638

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Abstract

The desire for maximally efficient transformations in complex molecule synthesis has contributed to a surge of interest in C–H functionalization methods development in recent years. In contrast to the steady stream of methodological reports, however, there are noticeably fewer studies comparing the efficacies of different C–H functionalization protocols on a single structurally intricate substrate. Recognizing the importance of heteroatom incorporation in complex molecule synthesis, this report discloses a comparative examination of diverse strategies for C–O, C–N, and C–X bond formation through late-stage C–H oxidation of the tricyclic cyanthiwigin natural product core. Methods for allylic C–H acetoxylation, tertiary C–H hydroxylation, tertiary C–H amination, tertiary C–H azidation, and secondary C–H halogenation are explored. These efforts highlight the robustness and selectivities of many well-established protocols for C–H oxidation when applied to a complex molecular framework, and the findings are relevant to chemists aiming to employ such strategies in the context of chemical synthesis.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/acs.joc.7b03291DOIArticle
http://pubs.acs.org/doi/10.1021/acs.joc.7b03291PublisherArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.joc.7b03291PublisherSupporting Information
ORCID:
AuthorORCID
Adams, Ashley M.0000-0003-0823-3709
Chiappini, Nicholas D.0000-0003-0469-1008
Du Bois, J.0000-0001-7847-1548
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2018 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: December 29, 2017; Published: January 9, 2018. This work was supported by the NSF under the CCI Center for Selective C–H Functionalization (CCHF), CHE-1700982. Additional financial support was provided by Caltech and Novartis. Dr. Xiangyou Xing and members of the CCHF are acknowledged for helpful discussions. The White group (UIUC) and the Sarpong group (UC Berkeley) are thanked for supplying the Fe(R,R-CF3-PDP) and Fe(S,S-PDP) catalysts, respectively. Dr. David VanderVelde (NMR), Dr. Mona Shahgholi and Naseem Torian (HRMS), and Dr. Michael K. Takase and Niklas Thompson (X-ray crystallography) are acknowledged for assistance with structural determination and characterization. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1700982
CaltechUNSPECIFIED
NovartisUNSPECIFIED
Issue or Number:6
Record Number:CaltechAUTHORS:20180109-144403638
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180109-144403638
Official Citation:Cyanthiwigin Natural Product Core as a Complex Molecular Scaffold for Comparative Late-Stage C–H Functionalization Studies. Kelly E. Kim, Ashley M. Adams, Nicholas D. Chiappini, J. Du Bois, and Brian M. Stoltz. The Journal of Organic Chemistry 2018 83 (6), 3023-3033 DOI: 10.1021/acs.joc.7b03291
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:84197
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:09 Jan 2018 23:03
Last Modified:03 Oct 2019 19:15

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