Investigation of functionalized α-chloroalkyllithiums for a stereospecific reagent-controlled homologation approach to the analgesic alkaloid (-)-epibatidine.

@article{Emerson2013InvestigationOF,
  title={Investigation of functionalized α-chloroalkyllithiums for a stereospecific reagent-controlled homologation approach to the analgesic alkaloid (-)-epibatidine.},
  author={Christopher R. Emerson and Lev N. Zakharov and Paul R Blakemore},
  journal={Chemistry},
  year={2013},
  volume={19 48},
  pages={
          16342-56
        }
}
Four putative functionalized α-chloroakyllithiums RCH2CHLiCl, where R=CHCH2(18 a), CCH (18 b), CH2OBn (18 c), and CH[O(CH2)2O] (18 d), were generated in situ by sulfoxide-lithium exchange from α-chlorosulfoxides, and investigated for the stereospecific reagent-controlled homologation (StReCH) of phenethyl and 2-chloropyrid-5-yl (17) pinacol boronic esters. Deuterium labeling experiments revealed that α-chloroalkyllithiums are quenched by proton transfer from their α-chlorosulfoxide precursors… CONTINUE READING

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References

Publications referenced by this paper.
SHOWING 1-6 OF 6 REFERENCES

Boronate 17 can be obtained from a variety of chemical suppliers (e.g., Aldrich, cat

P. R. Blakemore
  • Tetrahedron
  • 2002
VIEW 3 EXCERPTS
HIGHLY INFLUENTIAL

Heterocycles 2012 , 85 , 1 – 33 ; b ) T . Satoh

J. Mansilla Casatejada, T. G. Elford, R. P. Sonawane, V. K. Aggarwal
  • Org . Lett .
  • 2013

Recent examples of sulfoxide–lithium exchange for the synthesis of non-trivial organolithiums

P. J. Rayner, P. O Brien, R.A.J. Horan, J. Am
  • Synthesis 2012,
  • 2013
VIEW 2 EXCERPTS

The gauche effect in a - halogenated ( and related ) sulfoxides is prece - dented and often attributed to hyperconjugative stabilization with the s * SO orbital playing a major role , see : a ) M . P

H. Momochi, T. Satoh
  • Tetrahedron : Asymmetry
  • 2010

Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemeurj.org 16355 FULL PAPER Functionalized a-Chloroalkyllithiums

F. I. Carroll
  • Heterocycles
  • 2009
VIEW 1 EXCERPT

For studies establishing microscopic configurational stability for acyclic a - bromoalkyllithums , see : a ) R . W . Hoffmann , T . Ruhland , M . Bewersdorf

M. Duraisamy, J. Rachon, +3 authors H. M. Walborsky
  • J . Am . Chem . Soc .
  • 1976