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Total Synthesis and Characterization of 7-Hypoquinuclidonium Tetrafluoroborate and 7-Hypoquinuclidone BF_3 Complex

Liniger, Marc and VanderVelde, David G. and Takase, Michael K. and Shahgholi, Mona and Stoltz, Brian M. (2015) Total Synthesis and Characterization of 7-Hypoquinuclidonium Tetrafluoroborate and 7-Hypoquinuclidone BF_3 Complex. Journal of the American Chemical Society, 138 (3). pp. 969-974. ISSN 0002-7863. PMCID PMC4878439. https://resolver.caltech.edu/CaltechAUTHORS:20160119-141029568

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Abstract

Derivatives of the fully twisted bicyclic amide 7-hypoquinuclidone are synthesized using a Schmidt–Aubé reaction. Their structures were unambiguously confirmed by X-ray diffraction analysis and extensive spectroscopic characterization. Furthermore, the stability and chemical reactivity of these anti-Bredt amides are investigated. 7-Hypoquinuclidonium tetrafluoroborate is shown to decompose to a unique nitrogen bound amide–BF_3 complex of 7-hypoquinuclidone under anhydrous conditions and to react instantaneously with water making it one of the most reactive amides known to date.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.5b11750DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.5b11750PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.5b11750PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4878439/PubMed CentralArticle
ORCID:
AuthorORCID
VanderVelde, David G.0000-0002-2907-0366
Takase, Michael K.0000-0001-8365-3645
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2015 American Chemical Society. Received: November 9, 2015. Publication Date (Web): December 29, 2015. The authors wish to thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, the Caltech Center for Catalysis and Chemical Synthesis, and Caltech for financial support. M.L. thanks the Swiss National Science Foundation (SNSF) for a postdoctoral fellowship (P2EZP2_148751). Jonathan Rittle is acknowledged for assistance with the ATR-IR and the Peters group for using their equipment. We are indebted to Dr. Kousouke Tani and Dr. Michael Krout for taking the first steps in creating the twisted amide project and for establishing their synthesis, isolation and crystallization. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR01GM080269-01
AmgenUNSPECIFIED
Gordon and Betty Moore FoundationUNSPECIFIED
Caltech Center for Catalysis and Chemical SynthesisUNSPECIFIED
CaltechUNSPECIFIED
Swiss National Science Foundation (SNSF)P2EZP2_148751
Issue or Number:3
PubMed Central ID:PMC4878439
Record Number:CaltechAUTHORS:20160119-141029568
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160119-141029568
Official Citation:Total Synthesis and Characterization of 7-Hypoquinuclidonium Tetrafluoroborate and 7-Hypoquinuclidone BF3 Complex Marc Liniger, David G. VanderVelde, Michael K. Takase, Mona Shahgholi, and Brian M. Stoltz Journal of the American Chemical Society 2016 138 (3), 969-974 DOI: 10.1021/jacs.5b11750
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63769
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 Jan 2016 22:28
Last Modified:09 Mar 2020 13:19

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