Spongipyran synthetic studies. Total synthesis of (+)-spongistatin 2

Evolution of a convergent synthetic strategy to access (+)-spongistatin 2 ( 2), a potent cytotoxic marine macrolide, is described. Highlights of the synthesis include: development of a multicomponent dithiane-mediated linchpin union tactic, devised and implemented specifically for construction of th...

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Published in:Tetrahedron 2009-08, Vol.65 (33), p.6470-6488
Main Authors: Smith, Amos B., Lin, Qiyan, Doughty, Victoria A., Zhuang, Linghang, McBriar, Mark D., Kerns, Jeffrey K., Boldi, Armen M., Murase, Noriaki, Moser, William H., Brook, Christopher S., Bennett, Clay S., Nakayama, Kiyoshi, Sobukawa, Masao, Lee Trout, Robert E.
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cited_by cdi_FETCH-LOGICAL-c482t-85fa1761e09e3c208b4034d30127b88ca15af5b0792ed3232166ab307e753d9b3
cites cdi_FETCH-LOGICAL-c482t-85fa1761e09e3c208b4034d30127b88ca15af5b0792ed3232166ab307e753d9b3
container_end_page 6488
container_issue 33
container_start_page 6470
container_title Tetrahedron
container_volume 65
creator Smith, Amos B.
Lin, Qiyan
Doughty, Victoria A.
Zhuang, Linghang
McBriar, Mark D.
Kerns, Jeffrey K.
Boldi, Armen M.
Murase, Noriaki
Moser, William H.
Brook, Christopher S.
Bennett, Clay S.
Nakayama, Kiyoshi
Sobukawa, Masao
Lee Trout, Robert E.
description Evolution of a convergent synthetic strategy to access (+)-spongistatin 2 ( 2), a potent cytotoxic marine macrolide, is described. Highlights of the synthesis include: development of a multicomponent dithiane-mediated linchpin union tactic, devised and implemented specifically for construction of the spongistatin AB and CD spiro ring systems; application of a Ca II ion controlled acid promoted equilibration to set the thermodynamically less stable axial–equatorial stereogenicity in the CD spiroketal; use of sulfone addition/Julia methylenation sequences to unite the AB and CD fragments and introduce the C(44)–C(51) side chain; and fragment union and final elaboration to (+)-spongistatin 2 ( 2) exploiting Wittig olefination to unite the advanced ABCD and EF fragments, followed by regioselective Yamaguchi macrolactonization and global deprotection. Correction of the CD spiro ring stereogenicity was subsequently achieved via acid equilibration in the presence of Ca II ion to furnish (+)-spongistatin 2 ( 2). The synthesis proceeded with a longest linear sequence of 41 steps. [Display omitted]
doi_str_mv 10.1016/j.tet.2009.04.001
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title Spongipyran synthetic studies. Total synthesis of (+)-spongistatin 2
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