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. 2014 Oct 28;70(43):7942-7949.
doi: 10.1016/j.tet.2014.08.058.

Synthetic studies towards Zetekitoxin AB: preparation of 4,5-epi-11-hydroxy-saxitoxinol

Aaron D Pearson  1 , Robert M Williams  1
Affiliations

Synthetic studies towards Zetekitoxin AB: preparation of 4,5-epi-11-hydroxy-saxitoxinol

Aaron D Pearson et al. Tetrahedron. .

Abstract

A concise synthesis of 4,5-epi-11-hydroxy-saxitoxinol utilizing D-ribose to direct an asymmetric Mannich reaction. This approach allows many modes of reactivity, which can be used to access various analogs of saxitoxin.

Keywords: Diamino acid; Mannich reaction; Saxitoxin; Sodium channel; Zetekitoxin AB.

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Figures

Figure 1
Figure 1
Structures of Zetekitoxin AB (left) and saxitoxin (right)
Scheme 1
Scheme 1
Retrosythetic analysis of zetekitoxin AB
Scheme 2
Scheme 2
Preparation of Mannich product 12 from D-Ribose (8)
Scheme 3
Scheme 3
Elaboration of Mannich product 12 to ketone 15
Scheme 4
Scheme 4
Hypothetical formation of tricycle
Scheme 5
Scheme 5
Synthesis of oxazolidinone 19
Scheme 6
Scheme 6
Preparation of lactol 22
Scheme 7
Scheme 7
Two step installation of amine.
Scheme 8
Scheme 8
Reductive amination with oNB-amine
Scheme 9
Scheme 9
Installation and cyclization of the isothiourea
Scheme 10
Scheme 10
Potential cyclization pathways
Scheme 11
Scheme 11
Determination of the cyclization pathway
Scheme 12
Scheme 12
Cyclization of hemiaminal 30
Scheme 13
Scheme 13
Plan to epimerize C-5
Scheme 14
Scheme 14
Preparation of tricycle 44
Scheme 15
Scheme 15
Modes of reactivity of hemiaminal 30
See this image and copyright information in PMC

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