Unified synthesis of eudesmanolides, combining biomimetic strategies with homogeneous catalysis and free-radical chemistry

被引：119

作者：

Barrero, AF ^{[1
]}

Rosales, A ^{[1
]}

Cuerva, JM ^{[1
]}

Oltra, JE ^{[1
]}

机构：

[1] Univ Granada, Fac Sci, Dept Organ Chem, E-18071 Granada, Spain

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 11期

关键词：

D O I：

10.1021/ol034510k

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHIC] A general procedure for the synthesis of both 12,6- and 12,8-eudesmanolides has been developed. The key step is the titanocene-catalyzed radical cyclization of accessible epoxygermacrolides. The novel reagent 2,4,6-trimethyl-1-trimethylsilyipyridinium chloride, both compatible with oxiranes and capable of regenerating Cp2TiCl2 from Cp2Ti(Cl)H and Cp2Ti(Cl)OAc, played an important role in the catalytic cycle leading to exocyclic alkenes.

引用

页码：1935 / 1938

页数：4

共 35 条

[1] EUDESMANOLIDES AND OTHER CONSTITUENTS FROM ARTEMISIA-HERBA-ALBA [J].

AHMED, AA ;

ABOUELELA, M ;

JAKUPOVIC, J ;

ELDIN, AAS ;

SABRI, N .

PHYTOCHEMISTRY, 1990, 29 (11) :3661-3663

[2] STUDIES IN SYNTHESES OF SESQUITERPENE LACTONES .2. CHEMICAL TRANSFORMATION OF ALPHA-SANTONIN INTO REYNOSIN, SANTAMARINE, EPOXYSANTAMARINE AND 1BETA-HYDROXYARBUSCULIN-A [J].

ANDO, M ;

TAKASE, K .

TETRAHEDRON, 1977, 33 (21) :2785-2789

[3] STUDIES ON THE SYNTHESES OF SESQUITERPENE LACTONES .10. IMPROVED SYNTHESES OF (+)-TUBERIFERIN AND THE RELATED ALPHA-METHYLENE GAMMA-LACTONES AND THEIR BIOLOGICAL-ACTIVITIES [J].

ANDO, M ;

WADA, T ;

KUSAKA, H ;

TAKASE, K ;

HIRATA, N ;

YANAGI, Y .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (21) :4792-4796

[4] Preparation, stereochemistry, and cytotoxic activity of the melampolides from Mikania minima [J].

Barrero, AF ;

Oltra, JE ;

Rodríguez-García, I ;

Barragán, A ;

Alvarez, M .

JOURNAL OF NATURAL PRODUCTS, 2000, 63 (03) :305-307

[5] Effects of solvents and water in Ti(III)-mediated radical cyclizations of epoxygermacrolides.: Straightforward synthesis and absolute stereochemistry of (+)-3α-hydroxyreynosin and related eudesmanolides [J].

Barrero, AF ;

Oltra, JE ;

Cuerva, JM ;

Rosales, A .

JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (08) :2566-2571

[6] Synthesis of (+)-8-deoxyvernolepin and its 11,13-dihydroderivative.: A novel reaction initiated by sulfene elimination leads to the 2-oxa-cis-decalin skeleton [J].

Barrero, AF ;

Oltra, JE ;

Alvarez, M ;

Rosales, A .

JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (16) :5461-5469

[7] Approaches to the synthesis of 8-epi-vernolepin from germacrolides [J].

Barrero, AF ;

Oltra, JE ;

Barragán, A ;

Alvarez, M .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1998, (24) :4107-4113

[8] Palladium II promoted rearrangement of germacranolides. Synthesis of (+)-stoebenolide and (+)-dehydromelitensin. [J].

Barrero, AF ;

Oltra, JE ;

Alvarez, M .

TETRAHEDRON LETTERS, 1998, 39 (11) :1401-1404

[9]

BERMEJOBARRERA J, 1967, TETRAHEDRON LETT, V8, P3475

[10] SYNTHESIS OF THE REPORTED STRUCTURE OF HERBOLIDE-I AND ITS C-11 EPIMER FROM ARTEMISIN [J].

BLAY, G ;

CARDONA, L ;

GARCIA, B ;

PEDRO, JR .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (25) :7204-7208

← 1 2 3 4 →