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CC BY-ND-NC 4.0 · SynOpen 2018; 02(02): 0168-0175
DOI: 10.1055/s-0036-1591976
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Asymmetric and Regiospecific Synthesis of Isotopically Labelled Cyclopropane Fatty Acid (9R,10S)-Dihydrosterculic Acid: Overcoming Spontaneous Protonation During Lithium-Sulfoxide Exchange­

Samuel W. J. Shields
a   Carleton University, Department of Chemistry, 203 Steacie Building,, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, Canada
,
Peter H. Buist
a   Carleton University, Department of Chemistry, 203 Steacie Building,, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, Canada
b   Carleton University, Institute of Biochemistry, 209 Nesbitt Building, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, Canada   Email: jeff.manthorpe@carleton.ca
,
Jeffrey M. Manthorpe  *
a   Carleton University, Department of Chemistry, 203 Steacie Building,, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, Canada
b   Carleton University, Institute of Biochemistry, 209 Nesbitt Building, 1125 Colonel By Drive, Ottawa, Ontario, K1S 5B6, Canada   Email: jeff.manthorpe@carleton.ca
› Author AffiliationsThis research was supported by a Natural Sciences and Engineering Research Council of Canada (NSERC) Discovery Grant (P.H.B.), an NSERC Research Tools and Instrument Grant (P.H.B. and J.M.M.), the Canada Foundation for Innovation Leaders Opportunity Fund (J.M.M.) and Carleton University (J.M.M.).

Further Information

Publication History

Received: 12 January 2018

Accepted after revision: 14 March 2018

Publication Date:
08 June 2018 (online)

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Abstract

The total synthesis of isotopically labelled (9R,10S)-dihydro­sterculic acid, a usual cyclopropane fatty acid with biologically relevant toxicity upon desaturation in vivo, is reported. A diastereoselective Corey­–Chaykovsky reaction was employed to form the cyclopropane ring. Rapid quenching of a lithium-sulfoxide exchange was required to achieve the requisite high levels of deuterium incorporation.

Key words

lithium-sulfoxide exchange - deuterium labelling - asymmetric Corey–Chaykovsky cyclopropanation - cyclopropane fatty acids - mechanistic probes - fatty acid desaturation

Supporting Information

    Experimental procedures, spectral data, copies of 1H NMR and 13C NMR spectra are available.Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1591976.
  • Supporting Information
 

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