Spongipyran Synthetic Studies. Evolution of a Scalable Total Synthesis of (+)-Spongistatin 1.

Tetrahedron
Amos B SmithYasuharu Sakamoto

Abstract

Three syntheses of the architecturally complex, cytotoxic marine macrolide (+)-spongistatin 1 (1) are reported. Highlights of the first-generation synthesis include: use of a dithiane multicomponent linchpin coupling tactic for construction of the AB and CD spiroketals, and their union via a highly selective Evans boron-mediated aldol reaction en route to an ABCD aldehyde; introduction of the C(44)-C(51) side chain via a Lewis acid-mediated ring opening of a glucal epoxide with an allylstannane to assemble the EF subunit; and final fragment union via Wittig coupling of the ABCD and EF subunits to form the C(28)-C(29) olefin, followed by regioselective Yamaguchi macrolactonization and global deprotection. The second- and third- generation syntheses, designed with the goal of accessing one gram of (+)-spongistatin 1 (1), maintain both the first-generation strategy for the ABCD aldehyde and final fragment union, while incorporating two more efficient approaches for construction of the EF Wittig salt. The latter combine the original chelation-controlled dithiane union of the E- and F-ring progenitors with application of a highly efficient cyanohydrin alkylation to append the F-ring side chain, in conjunction with two independent ta...Continue Reading

References

Aug 17, 2004·Science·Alan B Northrup, David W C MacMillan
Feb 18, 2010·Tetrahedron·Amos B SmithRobert E Lee Trout

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Citations

Mar 27, 2013·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Wamtinga Richard SawadogoMarc Diederich
Feb 18, 2010·Tetrahedron·Amos B SmithRobert E Lee Trout
Sep 10, 2013·Chemistry : a European Journal·Sachin B NaruteChepuri V Ramana
Mar 15, 2015·Chemical Reviews·Guillaume EppeIlan Marek
Feb 23, 2013·Biochimica Et Biophysica Acta·Gordon M Cragg, David J Newman
May 24, 2016·Marine Drugs·Nelson G M GomesAlexander Kornienko
May 5, 2011·Journal of Chemical Information and Modeling·Ruoli BaiErnest Hamel
Jun 19, 2013·The Journal of Organic Chemistry·Guo-Jie JiangZhi-Xiang Yu
Jul 19, 2011·Journal of the American Chemical Society·Amos B SmithQunli Xu
Jan 20, 2011·Proceedings of the National Academy of Sciences of the United States of America·Amos B Smith, Won-Suk Kim
May 15, 2015·Natural Product Reports·Erik M LarsenRichard E Taylor
Aug 16, 2013·Beilstein Journal of Organic Chemistry·Kristin D Schleicher, Timothy F Jamison
Jan 13, 2011·Natural Product Reports·Jonathan C Morris, Andrew J Phillips
Oct 8, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Marc LinigerKarl-Heinz Altmann
Jan 13, 2021·Chemistry : a European Journal·Cédric TresseStéphanie Norsikian
Jan 27, 2019·Journal of the American Chemical Society·Benjamin J Huffman, Ryan A Shenvi
Feb 27, 2018·The Journal of Organic Chemistry·Minh H NguyenAmos B Smith
Feb 13, 2018·Journal of Natural Products·John H MillerPeter T Northcote

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