Total synthesis of (+)-papulacandin D

Total synthesis of (+)-papulacandin D

A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain....

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Veröffentlicht in:Tetrahedron 2010-06, Vol.66 (26), p.4745-4759
Hauptverfasser: Denmark, Scott E., Kobayashi, Tetsuya, Regens, Christopher S.
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Sprache:eng
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Asymmetric allylation
C-Arylglycosides
Silicon-based cross-coupling
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container_end_page 4759
container_issue 26
container_start_page 4745
container_title Tetrahedron
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creator Denmark, Scott E.
Kobayashi, Tetsuya
Regens, Christopher S.
description A total synthesis of (+)-papulacandin D has been achieved in 31 steps, in a 9.2% overall yield from commercially available materials. The synthetic strategy divided the molecule into two nearly equal sized subunits, the spirocyclic C-arylglycopyranoside and the polyunsaturated fatty acid side-chain. The C-arylglycopyranoside was prepared in 11 steps in a 30% overall yield from triacetoxyglucal. The fatty acid side-chain was also prepared in 11 steps in a 30% overall yield from geraniol. The key strategic transformations in the synthesis are: (1) a palladium-catalyzed, organosilanolate-based cross-coupling reaction of a dimethylglucal-silanol with an electron-rich and sterically hindered aromatic iodide and (2) a Lewis-base catalyzed, enantioselective allylation reaction of a dienal and allyltrichlorosilane. A critical element in the successful execution of the synthesis was the development of a suitable protecting group strategy that satisfied a number of stringent criteria. [Display omitted]
doi_str_mv 10.1016/j.tet.2010.03.093
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subjects Asymmetric allylation
C-Arylglycosides
Silicon-based cross-coupling
title Total synthesis of (+)-papulacandin D
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