Asymmetric Synthesis of ( - )-Swainsonine

Lindsay, Karl B.; Pyne, Stephen G.

doi:10.1071/ch04009

Cited by 31 publications

(8 citation statements)

References 20 publications

(32 reference statements)

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“…The known amino-tetraol 2, 17 obtained from the borono-Mannich reaction of L-xylose, allylamine and (E)-styrene boronic acid, was converted to oxazolidin-2-one 3 upon treatment with triphosgene under basic conditions (Scheme 1). 13,14 The triol 4 was readily converted to its O-trityl derivative 4 in 87% yield under standard conditions. 17 Under basic O-benzylation reaction conditions 17 compound 4 gave a mixture of the corresponding di-O-benzyl-oxazolidin-2-one 5 and the oxazin-2-one 6 (Scheme 1).…”

Section: Resultsmentioning

confidence: 99%

“…Alternatively, 7 could be more readily obtained by treating a mixture of 5 and 6 with Grubbs' second generation ruthenium catalyst followed by a relatively easier separation of 7 (68%) from the pyrrolo[1, 2-c]oxazin-1-one 8 (20%) (Scheme 1). Based on our previous work, 13,14,19 and that of Parsons, 20,21 we expected that the syn-dihydroxylation (DH) of 7 would furnished the corresponding diol with the desired stereochemistry for the synthesis of the target alkaloid. In the event, the osmium(VIII)-catalysed syn-DH of 7 furnished the desired diol 9 accompanied by 17% of its diastereomeric diol in 84% yield after purification of the crude reaction mixture by column chromatography (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

“…9 Because of its unique structure and biological activities many syntheses of castanospermine have been reported. 10 As part of our program concerned with the synthesis of polyhydroxylated indolizidine and pyrrolizidine alkaloids [11][12][13][14][15][16][17][18][19] we report here a 11-step synthesis of castanospermine from L-xylose. This synthesis demonstrates the versatility and flexibility of our earlier synthetic strategy for preparing polyhydroxyindolizidines.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of castanospermine

et al. 2008

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The diastereoselective synthesis of castanospermine is described in 11 synthetic steps from L-xylose. The borono-Mannich reaction between L-xylose, allylamine and (E)-styrene boronic acid gives a tetrahydroxy amine with the desired configurations for C-6, C-7, C-8 and C-8a in the target molecule. A novel pyrrolo[1,2-c]oxazol-3-one precursor was employed to allow for the control of pi-facial diastereoselectivity in an osmium(VIII)-catalysed syn-dihydroxylation (DH) reaction. A regioselective ringopening of the cyclic sulfate derivative of the resulting diol then secured the C-1 hydroxyl group of castanospermine with the correct configuration. A Mitsunobu cyclization then provided di-O-benzyl castanospermine and ultimately the final target alkaloid.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of castanospermine

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“…Oddly enough, neither the optical rotation nor the absolute configuration of the natural product have been reported, although the absolute configuration shown in 289 seems plausible by analogy with (−)-lasubine II 272. 12…”

Section: Lythraceae Alkaloidsmentioning

confidence: 99%

Indolizidine and quinolizidine alkaloids

Michael

2007

Nat. Prod. Rep.

252

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This review covers the isolation, structure determination, synthesis, chemical transformations and biological activity of indolizidine and quinolizidine alkaloids. Included in the review are the hydroxylated indolizidines lentiginosine, swainsonine, castanospermine and their analogues; alkaloids from animal sources, including ants, amphibians and beetles; indolizidine alkaloids from the genera Polygonatum, Prosopis and Elaeocarpus; indolizidine and phenanthroindolizidine alkaloids; alkylquinolizidine alkaloids, including myrtine, epimyrtine, plumerinine and Lycopodium metabolites; Lythraceae and Nuphar alkaloids; lupine alkaloids; and alkaloids from marine sources. 150 references are cited.

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“…We have employed 1,2-amino alcohols that were prepared from the aminolysis of chiral vinyl epoxides, to the synthesis of (-)-swainsonine 9 and its epimers [17,18] and 1,7-di-epi-australine and 7-epi-australine [19,20]. Our first synthesis of swainsonine is outlined in Scheme 2 [17].…”

Section: Synthesis Of Polyhydroxlated Alkaloids Via the Aminolysis Ofmentioning

confidence: 99%

Exploiting the borono-Mannich reaction in bioactive alkaloid synthesis

Pyne

Davis

et al. 2008

Pure and Applied Chemistry

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Abstract:We have demonstrated that the borono-Mannich reaction is a versatile and efficient reaction for the diastereoselective preparation of chiral 1,2-amino alcohols. These Mannich products are valuable starting materials as shown in this report by the synthesis of bioactive polyhydroxylated pyrrolizidine and indolizidine alkaloids. Initial studies, directed at the more complex Stemona alkaloids and using the borono-Mannich reaction on cyclic N-acyliminium ions, are encouraging, as demonstrated by the synthesis of the pyrido[1,2-a]azepine core structure of stemocurtisinol.

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Asymmetric Synthesis of ( - )-Swainsonine

Abstract: This paper describes a new synthesis of (-)-swainsonine via the ring-closing metathesis reaction of a substituted 3-allyl-4-vinyl-2-oxazolindinone and subsequent diastereoselective syn-dihydroxylation of the resulting pyrrolo[1,2-c]oxazol-3-one. Keywords CMMB

Cited by 31 publications

References 20 publications

Synthesis of castanospermine

Synthesis of castanospermine

Indolizidine and quinolizidine alkaloids

Exploiting the borono-Mannich reaction in bioactive alkaloid synthesis

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