Anodic fragmentation of catharanthine and coupling with vindoline. Formation of anhydrovinblastine

被引：22

作者：

Tabakovic, I ^{[1
]}

Gunic, E ^{[1
]}

Juranic, I ^{[1
]}

机构：

[1] UNIV BELGRADE, FAC CHEM, YU-11000 BELGRADE, YUGOSLAVIA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1997年 / 62卷 / 04期

关键词：

D O I：

10.1021/jo9621128

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The anodic oxidation of catharanthine (Cath) in the presence of vindoline (Vind) performed in MeCN-Et(4)NClO(4) at a controlled potential yields (16'S)- and (16'R)-anhydrovinblastine (AVBL) in s 4.3:1 ratio. The favorable stereoselectivity found at room temperature is rationalized by proposing the coupling of generated dication 1a(++) and Vind at the electrode surface. The mechanism of the overall fragmentation/coupling reaction was studied using electrochemical techniques and the technique of homogeneous redox catalysis. It was concluded that the rate-determining step in the overall reaction is the first electron transfer leading to Cath(.+). MO calculations support the proposed mechanism and provide the evidence that C16-C21 bond fragmentation is a homolytic process.

引用

页码：947 / 953

页数：7

共 39 条

[11] ELECTROCHEMICAL SYNTHESIS OF ANHYDROVINBLASTINE [J].

GUNIC, E ;

TABAKOVIC, I ;

GASIC, MJ .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (19) :1496-1497

[12] HETEROGENEOUS RATES OF ELECTRON-TRANSFER - APPLICATION OF CYCLIC VOLTAMMETRIC TECHNIQUES TO IRREVERSIBLE ELECTROCHEMICAL PROCESSES [J].

KLINGER, RJ ;

KOCHI, JK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (14) :4790-4798

[13]

Kuehne M. E., 1990, ALKALOIDS, P77

[14] ENANTIOSELECTIVE SYNTHESES OF VINBLASTINE, LEUROSIDINE, VINCOVALINE, AND 20'-EPI-VINCOVALINE [J].

KUEHNE, ME ;

MATSON, PA ;

BORNMANN, WG .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (02) :513-528

[15] PLANT-CELL CULTURE COMBINED WITH CHEMISTRY - A POWERFUL ROUTE TO COMPLEX NATURAL-PRODUCTS [J].

KUTNEY, JP .

ACCOUNTS OF CHEMICAL RESEARCH, 1993, 26 (10) :559-566

[16] BIOSYNTHESIS AND SYNTHESIS OF INDOLE AND BISINDOLE ALKALOIDS IN PLANT-CELL CULTURES - A PERSONAL OVERVIEW [J].

KUTNEY, JP .

NATURAL PRODUCT REPORTS, 1990, 7 (02) :85-103

[17] TOTAL SYNTHESIS OF INDOLE AND DIHYDROINDOLE ALKALOIDS .9. STUDIES ON SYNTHESIS OF BISINDOLE ALKALOIDS IN VINBLASTINE-VINCRISTINE SERIES - BIOGENETIC APPROACH [J].

KUTNEY, JP ;

HIBINO, T ;

JAHNGEN, E ;

OKUTANI, T ;

RATCLIFFE, AH ;

TREASURYWALA, AM ;

WUNDERLY, S .

HELVETICA CHIMICA ACTA, 1976, 59 (08) :2858-2882

[18] CHRONOPOTENTIOMETRIC STUDIES ON THE OXIDATION OF FERROCENE, RUTHENOCENE, OSMOCENE AND SOME OF THEIR DERIVATIVES [J].

KUWANA, T ;

BUBLITZ, DE ;

HOH, G .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1960, 82 (22) :5811-5817

[19] APPLICATION OF A MODIFICATION OF POLONOVSKI REACTION TO SYNTHESIS OF VINBLASTINE-TYPE ALKALOIDS [J].

LANGLOIS, N ;

GUERITTE, F ;

LANGLOIS, Y ;

POTIER, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (22) :7017-7024

[20] SYNTHESIS OF THE ANTITUMOR BISINDOLE ALKALOID VINBLASTINE - DIASTEREOSELECTIVITY AND SOLVENT EFFECT ON THE STEREOCHEMISTRY OF THE CRUCIAL C-15-C-18' BOND [J].

MAGNUS, P ;

STAMFORD, A ;

LADLOW, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (22) :8210-8212

← 1 2 3 4 →