Polyhydroxylated pyrrolizidine alkaloids from transannular iodoaminations: application to the asymmetric syntheses of (-)-hyacinthacine A1, (-)-7a-epi-hyacinthacine A1, (-)-hyacinthacine A2, and (-)-1-epi-alexine

被引：45

作者：

Brock, E. Anne ^{[1
]}

Davies, Stephen G. ^{[1
]}

Lee, James A. ^{[1
]}

Roberts, Paul M. ^{[1
]}

Thomson, James E. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Chem Res Lab, Oxford OX1 3TA, England

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2013年 / 11卷 / 19期

关键词：

RING-CLOSING METATHESIS; DIASTEREOSELECTIVE CONJUGATE ADDITION; JASPINE-B PACHASTRISSAMINE; HOMOCHIRAL LITHIUM AMIDES; D-LYXO-PHYTOSPHINGOSINE; CONCISE TOTAL-SYNTHESIS; (2S; 3R)-3-AMINO-2-HYDROXYDECANOIC ACID; STEREOSELECTIVE-SYNTHESIS; STRUCTURAL CONFIRMATION; GLYCOSIDASE INHIBITORS;

D O I：

10.1039/c3ob40205c

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The transannular iodoamination of substituted 1,2,3,4,7,8-hexahydroazocine scaffolds has been developed into a versatile, diastereodivergent route to enable the synthesis of a range of pyrrolizidine alkaloids, as demonstrated by the syntheses of (-)-hyacinthacine A1, (-)-7a-epi-hyacinthacine A1, (-)-hyacinthacine A2, and (-)-1-epi-alexine. The requisite 1,2,3,4,7,8-hexahydroazocines (bearing either an N-alpha-methyl-p-methoxybenzyl group or no N-substituent) were readily prepared via conjugate addition of lithium (R)-N-but-3-enyl-N-(a-methyl-p-methoxybenzyl) amide to either tert-butyl (4S,5R,E)-4,5-dihydroxy-4,5-O-isopropylidene-2,7-dienoate (derived from D-ribose) or tert-butyl (S, S, E)-4,5-dihydroxy-4,5-O-isopropylidene-2,7-dienoate (derived from L-tartaric acid) coupled with in situ enolate oxidation with (-)-camphorsulfonyloxaziridine, followed by ring-closing metathesis with Grubbs I catalyst. Subsequent reaction with I-2 resulted in transannular iodoamination (accompanied by concomitant loss of the N-alpha-methyl-p-methoxybenzyl group for tertiary amine substrates) to give the corresponding pyrrolizidine scaffolds.

引用

页码：3187 / 3202

页数：16

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