Organic Letters
Letter
In conclusion, we have completed the first total synthesis of
two stereoisomers of laingolide B, (−)-(2R,9S)-6a and
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+)-(2S,9S)-6b, in a 12-step longest linear sequence from the
17
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known (S)-12 in 9−10% overall yields. The RCM−alkene
isomerization strategy has been demonstrated as a powerful tool
in the construction of this unique 15-membered N-Me-enamide-
containing macrolide. With the two synthesized stereoisomers, it
(5) For the bioactivity of palmyrolide A and the synthetic analogues,
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1
3
has been confirmed by comparison of the C NMR data that the
naturally occurring laingolide B possesses a 2,9-anti-Me/t-Bu
relationship, while comparison of the optical rotation data
determines the (2S,9R) absolute configuration for the natural
laingolide B. Assignment of the stereochemistry of laingolide B
should facilitate determination of the absolute configuration of
the related laingolide congeners. Our results on the total
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(7) For the isolation and the proposed planar structures of laingolide A
12
and madangolide, see Klein, D.; Braekman, J. C.; Daloze, D.; Hoffmann,
synthesis of laingolide A (2) and laingolide (3) will be disclosed
L.; Castillo, G.; Demoulin, V. J. J. Nat. Prod. 1999, 62, 934−936.
in due course.
(8) For the total synthesis of laingolide A diastereomers, see Pomey,
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ASSOCIATED CONTENT
Supporting Information
■
(9) For the isolation and the proposed planar structure of laingolide B,
see Matthew, S.; Salvador, L. A.; Schupp, P. J.; Paul, V. J.; Luesch, H. J.
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*
S
(
10) For a synthesis of the C1−C9 fragment of laingolide B, see
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(11) For the isolation and the structure of apratoxin A, see Luesch, H.;
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Detailed experimental procedures, compound character-
ization data, and copies of original H and C NMR
1
13
2
(
001, 123, 5418−5423.
12) Lai, Y. Ph.D. Thesis, The Hong Kong University of Science and
Technology, 2015.
AUTHOR INFORMATION
■
*
(13) Graf, K. M.; Tabor, M. G.; Brown, M. L.; Paige, M. Org. Lett. 2009,
11, 5382−5385.
(14) (a) Myers, A. G.; Yang, B. H.; Chen, H.; Gleason, J. L. J. Am. Chem.
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496−6511.
15) For reviews on B-alkyl Suzuki−Miyaura cross-coupling reaction,
Notes
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The authors declare no competing financial interest.
2
011, 50, 6722−6737. (e) Jana, R.; Pathak, T. P.; Sigman, M. S. Chem.
ACKNOWLEDGMENTS
This work is supported in part by a General Research Fund grant
601211) from the Research Grant Council, The Hong Kong
■
(
Rev. 2011, 111, 1417−1492. (f) Seidel, G.; Fu
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