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Enantioselective and diastereoselective azo-coupling/iminium-cyclizations: a unified strategy for the total syntheses of (-)-psychotriasine and (+)-pestalazine B.

ABSTRACT: We report a unified strategy for the total syntheses of (-)-psychotriasine and (+)-pestalazine B based on the advanced intermediates of 3?-amino-hexahydropyrrolo[2,3-b]indole. To construct these structural motifs, a cascade reaction involving a BINOL-derived phosphoric anion-paired catalyst for enantioselective or diastereoselective azo-coupling/iminium-cyclizations was developed. The remaining key steps of the synthesis involve a sterically hindered amination via hypervalent iodine reagents and the Larock annulation. These transformations enable a general approach to the syntheses of indole alkaloids containing a 3?-amino-hexahydropyrrolo[2,3-b]indole motif and could be further applied to build a natural product-based library.

SUBMITTER: Li Q

PROVIDER: S-EPMC5659145 | biostudies-literature | 2015 Jun

REPOSITORIES: biostudies-literature

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Enantioselective and diastereoselective azo-coupling/iminium-cyclizations: a unified strategy for the total syntheses of (-)-psychotriasine and (+)-pestalazine B.

Li Qi Q Xia Tingting T Yao Licheng L Deng Haiteng H Liao Xuebin X

Chemical science 20150505 6

We report a unified strategy for the total syntheses of (-)-psychotriasine and (+)-pestalazine B based on the advanced intermediates of 3α-amino-hexahydropyrrolo[2,3-<i>b</i>]indole. To construct these structural motifs, a cascade reaction involving a BINOL-derived phosphoric anion-paired catalyst for enantioselective or diastereoselective azo-coupling/iminium-cyclizations was developed. The remaining key steps of the synthesis involve a sterically hindered amination <i>via</i> hypervalent iodin ...[more]

PMID: 29511522

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