Synthesis of phytuberin.: 4-endo-tet acid-catalyzed cyclization of α-hydroxy epoxides

被引：17

作者：

Prangé, T

Rodríguez, MS

Suárez, E

机构：

[1] CSIC, Inst Prod Nat & Agrobiol, Tenerife 38206, Spain

[2] Univ La Laguna, Dept Quim Organ, Tenerife, Spain

[3] Univ Paris 11, LURE, F-91405 Orsay, France

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 11期

关键词：

D O I：

10.1021/jo034129d

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The total synthesis of phytuberin, a phytoalexin of the Solanum genus, from (-)-alpha-santonin is reported. The key steps include (a) reductive cleavage of the C-O bond of the gamma-lactone with concomitant protection of the C1 double bond, (b) Sharpless stereocontrolled hydroxy-assisted epoxidation of allylic alcohol 6 and simultaneous deprotection of the C1 double bond, (c) a rare 4-endo-tet acid-catalyzed cyclization of an alpha-hydroxy epoxide, and (d) an unprecedented 4-exo selenocyclization of a homoallylic alcohol.

引用

收藏

页码：4422 / 4431

页数：10

相关论文

共 88 条

[11] SPALTUNG VON DISULFIDEN ZU ARSEN(III)-MERCAPTIDEN [J].

BIELIG, HJ ;

LUTZEL, G ;

REIDIES, A .

CHEMISCHE BERICHTE-RECUEIL, 1956, 89 (03) :775-792

[12] CHEMISTRY OF INSECT ANTIFEEDANTS FROM AZADIRACHTA-INDICA .1. CONVERSION FROM THE AZADIRACHTIN TO THE AZADIRACHTININ SKELETONS [J].

BILTON, JN ;

JONES, PS ;

LEY, SV ;

ROBINSON, NG ;

SHEPPARD, RN .

TETRAHEDRON LETTERS, 1988, 29 (15) :1849-1852

[13] SYNTHETIC ROUTES TO TETRAHYDROFURAN, TETRAHYDROPYRAN, AND SPIROKETAL UNITS OF POLYETHER ANTIBIOTICS AND A SURVEY OF SPIROKETALS OF OTHER NATURAL-PRODUCTS [J].

BOIVIN, TLB .

TETRAHEDRON, 1987, 43 (15) :3309-3362

[14] A CONVENIENT, STEREOSPECIFIC SYNTHESIS OF (-)-PHYTUBERIN FROM (-)-2-CARONE [J].

CAINE, D ;

SMITH, TL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (25) :7568-7570

[15] CYCLOFUNCTIONALIZATION OF UNSATURATED-ACIDS WITH BENZENESELENENYL CHLORIDE - KINETIC AND THERMODYNAMIC ASPECTS OF THE RULES FOR RING-CLOSURE [J].

CLIVE, DLJ ;

RUSSELL, CG ;

CHITTATTU, G ;

SINGH, A .

TETRAHEDRON, 1980, 36 (10) :1399-1408

[16] METABOLITES FROM MICROBIALLY INFECTED POTATO .1. STRUCTURE OF PHYTUBERIN [J].

COXON, DT ;

PRICE, KR ;

HOWARD, B ;

CURTIS, RF .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1977, (01) :53-59

[17] Molecular orbital studies of the intramolecular reaction of protonated cis- and trans-3,4-epoxypentan-1-ol [J].

Coxon, JM ;

Morokuma, K ;

Thorpe, AJ ;

Whalen, D .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (12) :3875-3883

[18] Ab initio study of intramolecular ring cyclization of protonated and BF3-coordinated trans- and cis-4,5-epoxyhexan-1-ol [J].

Coxon, JM ;

Thorpe, AJ .

JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (15) :5530-5541

[19] 1,3-transposition of primary allylic alcohols: Synthesis of optically active secondary and tertiary allylic alcohols [J].

Dorta, RL ;

Rodriquez, MS ;

Salazar, JA ;

Suarez, E .

TETRAHEDRON LETTERS, 1997, 38 (26) :4675-4678

[20] SYNTHESIS OF UNDECULOFURANOSIDE DERIVATIVES OF THE HERBICIDINS AND OF ANALOGS [J].

EMERY, F ;

VOGEL, P .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (18) :5843-5854

← 1 2 3 4 5 6 7 8 9 →