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Diastereoselective concise syntheses of the polyhydroxylated alkaloids DMDP and DAB

Journal Article


Abstract


  • A diastereoselective concise synthesis of the iminosugars DMDP and DAB is presented starting from l-xylose and affording the two alkaloids in good yields of 35% and 22% over seven and eight steps, respectively. The Petasis borono–Mannich reaction of 3,5-di-O-benzyl-l-xylofuranose with benzylamine and (E)-styrylboronic acid served as the nitrogen-introducing key step furnishing the new C–N bond in an entirely diastereoselective manner. A chemo- and regioselective O-mesylation followed by an intramolecular SN2-cyclisation allowed the formation of the pyrrolidine ring. Ozonolysis of the styryl double bond and subsequent reduction to form the C-5 hydroxymethyl substituent followed by hydrogenolysis of the benzyl protecting groups concluded the DMDP synthesis. Furthermore, an unexpected fragmentation process during the ozonolysis reaction also gave access to the C-5 decarbinolated DMDP derivative DAB.

UOW Authors


Publication Date


  • 2014

Citation


  • Bouillon, M. & Pyne, S. G. (2014). Diastereoselective concise syntheses of the polyhydroxylated alkaloids DMDP and DAB. Tetrahedron Letters, 55 (2), 475-478.

Scopus Eid


  • 2-s2.0-84890786764

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/1361

Has Global Citation Frequency


Number Of Pages


  • 3

Start Page


  • 475

End Page


  • 478

Volume


  • 55

Issue


  • 2

Place Of Publication


  • United Kingdom

Abstract


  • A diastereoselective concise synthesis of the iminosugars DMDP and DAB is presented starting from l-xylose and affording the two alkaloids in good yields of 35% and 22% over seven and eight steps, respectively. The Petasis borono–Mannich reaction of 3,5-di-O-benzyl-l-xylofuranose with benzylamine and (E)-styrylboronic acid served as the nitrogen-introducing key step furnishing the new C–N bond in an entirely diastereoselective manner. A chemo- and regioselective O-mesylation followed by an intramolecular SN2-cyclisation allowed the formation of the pyrrolidine ring. Ozonolysis of the styryl double bond and subsequent reduction to form the C-5 hydroxymethyl substituent followed by hydrogenolysis of the benzyl protecting groups concluded the DMDP synthesis. Furthermore, an unexpected fragmentation process during the ozonolysis reaction also gave access to the C-5 decarbinolated DMDP derivative DAB.

UOW Authors


Publication Date


  • 2014

Citation


  • Bouillon, M. & Pyne, S. G. (2014). Diastereoselective concise syntheses of the polyhydroxylated alkaloids DMDP and DAB. Tetrahedron Letters, 55 (2), 475-478.

Scopus Eid


  • 2-s2.0-84890786764

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/1361

Has Global Citation Frequency


Number Of Pages


  • 3

Start Page


  • 475

End Page


  • 478

Volume


  • 55

Issue


  • 2

Place Of Publication


  • United Kingdom