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Convergent Total Synthesis of Murisolin
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Conclusions
In conclusion, a novel approach to the synthesis of an-
nonaceous acetogenin natural products by CM carbon
backbone assembly/late-stage THF formation has been
demonstrated by application in the total synthesis of muri-
solin with a longest linear sequence of just nine steps. The
route described herein is the shortest and most efficient re-
ported to date and serves to further validate the powerful
utility of olefin metathesis in acetogenin synthesis.[18] The
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make it broadly applicable in the efficient synthesis of other
acetogenins and more complex oxacyclic natural products.
These studies are ongoing and will be reported in due
course.
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[9] Prepared in gram quantities with high enantiopurity (Ͼ99:1er)
from commercially available divinyl carbinol by modified
Sharpless asymmetric epoxidation with the use of cumene hy-
droperoxide instead of tert-butylhydroperoxide, see: A. Ro-
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Supporting Information (see footnote on the first page of this arti-
cle): Experimental procedures, characterization data, and 1H and
13C NMR spectra for 1, (E)-2, 3, 4, 6, 7, 9, 11, and 12.
Acknowledgments
[11] For the preparation of 10, see: J. D. White, T. C. Somers, G. N.
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Financial support of this research by the National Science Founda-
tion (CHE-0848128) and the Sherman Fairchild Foundation is
gratefully acknowledged. Mass spectroscopic data were obtained at
the University of Massachusetts Mass Spectrometry Facility, which
is supported, in part, by the National Science Foundation.
[12] The general strategy outlined in Scheme 2 (alkylation of the
enolate of 10 followed by oxidation/elimination) is commonly
employed for the introduction of the γ-methylbutenolide sub-
unit of acetogenins. For recent examples of similar approaches
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Received: June 17, 2010
Published Online: September 22, 2010
Eur. J. Org. Chem. 2010, 5943–5945
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