Total synthesis of brasoside and littoralisone

被引：174

作者：

Mangion, IK ^{[1
]}

MacMillan, DWC ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2005年 / 127卷 / 11期

关键词：

D O I：

10.1021/ja050064f

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first total syntheses of littoralisone (1) and brasoside (2) have been achieved in 13 overall steps. Both natural products are forged from a common intermediate which is rapidly assembled using organocatalytic technology, including a proline-catalyzed α-aminoxylation and a contra-thermodynamic intramolecular Michael addition. Application of the two-step carbohydrate synthesis technology has enabled to access a selectively substituted glucose derivative for use as an intramolecular cycloaddition tether. This synthesis culminates with an intramolecular [2+2] photocycloaddition that serves to support the proposed biosynthetic origins of 1 from 2. Copyright © 2005 American Chemical Society.

引用

页码：3696 / 3697

页数：2

共 18 条

[1] The direct and enantioselective organocatalytic α-oxidation of aldehydes [J].

Brown, SP ;

Brochu, MP ;

Sinz, CJ ;

MacMillan, DWC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (36) :10808-10809

[2]

Buchi G., 1970, J AM CHEM SOC, V92, P2165

[3]

BUZOGANY K, 1983, FARM BUCHUREST, V31, P129

[4] IRIDOIDS - STEREOSPECIFIC SYNTHESIS OF FUNCTIONALIZED CYCLOPENTANOID INTERMEDIATES VIA BICYCLO[2.2.1]HEPTANONES [J].

CALLANT, P ;

STORME, P ;

VANDEREYCKEN, E ;

VANDEWALLE, M .

TETRAHEDRON LETTERS, 1983, 24 (51) :5797-5800

[5] Catalytic asymmetric intramolecular Michael reaction of aldehydes [J].

Fonseca, MTH ;

List, B .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (30) :3958-3960

[6] VEBRASIDE, AN IRIDOID GLUCOSIDE FROM VERBENA-BRASILIENSIS [J].

FRANKE, A ;

RIMPLER, H .

PHYTOCHEMISTRY, 1987, 26 (11) :3015-3020

[7] Direct proline catalyzed asymmetric α-aminooxylation of aldehydes [J].

Hayashi, Y ;

Yamaguchi, J ;

Hibino, K ;

Shoji, M .

TETRAHEDRON LETTERS, 2003, 44 (45) :8293-8296

[8] Littoralisone, a novel neuritogenic iridolactone having an unprecedented heptacyclic skeleton including four- and nine-membered rings consisting of glucose from Verbena littoralis [J].

Li, YS ;

Matsunaga, K ;

Ishibashi, M ;

Ohizumi, Y .

JOURNAL OF ORGANIC CHEMISTRY, 2001, 66 (06) :2165-2167

[9] Two-step synthesis of carbohydrates by selective aldol reactions [J].

Northrup, AB ;

MacMillan, DWC .

SCIENCE, 2004, 305 (5691) :1752-1755

[10] Enantioselective organocatalytic direct aldol reactions of α-oxyaldehydes:: Step one in a two-step synthesis of carbohydrates [J].

Northrup, AB ;

Mangion, IK ;

Hettche, F ;

MacMillan, DWC .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (16) :2152-2154

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