Zirconocene-mediated cyclization of 2-bromo alpha,omega-dienes

被引：24

作者：

Millward, DB ^{[1
]}

Waymouth, RM ^{[1
]}

机构：

[1] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94305

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 06期

关键词：

D O I：

10.1021/om960870i

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

When it is first treated with n-butyllithium at -78 degrees C, zirconocene dichloride is an effective reagent for the cyclization of some 2-bromo alpha,omega-dienes at 25 degrees C. The products are carbo- and heterocyclic five-membered rings with adjacent methylene and methyl substituents. Reductive cyclization to form zirconacyclopentanes, followed by beta-bromo elimination, is indicated as the order of steps in the reaction mechanism. Use of catalytic zirconocene dichloride with excess butylmagnesium chloride in diethyl ether at 25 degrees C is effective only for cyclization of 2-bromo-1,6-heptadiene.

引用

收藏

页码：1153 / 1158

页数：6

相关论文

共 30 条

[1] METHYLENOMYCIN-B - AN EFFICIENT SYNTHESIS FROM (2-BUTYNE)HEXACARBONYLDICOBALT [J].

BILLINGTON, DC ;

PAUSON, PL .

ORGANOMETALLICS, 1982, 1 (12) :1560-1561

[2] TOTAL SYNTHESIS OF (+)-LYCORICIDINE AND ITS 2-EPIMER FROM D-GLUCOSE [J].

CHIDA, N ;

OHTSUKA, M ;

OGAWA, S .

JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (16) :4441-4447

[3] STEREOSELECTIVE SYNTHESIS OF TETRAHYDROFURANS AND TETRAHYDROPYRANS BY NI(0) PROMOTED TANDEM CYCLIZATION-CARBONYLATION [J].

DELGADO, A ;

LLEBARIA, A ;

CAMPS, F ;

MORETO, JM .

TETRAHEDRON LETTERS, 1994, 35 (23) :4011-4014

[4] RHODIUM-CATALYZED AND PALLADIUM-CATALYZED FORMATION OF CONJUGATED MONO-EXOCYCLIC AND BIS-EXOCYCLIC DIENES - 5-EXO-TRIG-VERSUS 6-ENDO-TRIG CYCLIZATIONS [J].

GRIGG, R ;

STEVENSON, P ;

WORAKUN, T .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (16) :1073-1075

[5] THE REGIOSELECTIVITY OF RHODIUM AND PALLADIUM-CATALYZED CYCLIZATIONS OF 2-BROMO-1,6-DIENES AND 2-BROMO-1,7-DIENES [J].

GRIGG, R ;

STEVENSON, P ;

WORAKUN, T .

TETRAHEDRON, 1988, 44 (07) :2033-2048

[6] Titanocene-catalyzed cyclocarbonylation of enynes to cyclopentenones [J].

Hicks, FA ;

Kablaoui, NM ;

Buchwald, SL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (39) :9450-9451

[7] STEREOSELECTIVE CYCLIZATION VIA ZIRCONOCENE-CATALYZED INTRAMOLECULAR OLEFIN ALLYLATION [J].

KNIGHT, KS ;

WAYMOUTH, RM .

ORGANOMETALLICS, 1994, 13 (07) :2575-2577

[8] MECHANISM AND STEREOCHEMISTRY OF THE ZIRCONOCENE-CATALYZED CYCLOMAGNESIATION OF DIENES [J].

KNIGHT, KS ;

WANG, D ;

WAYMOUTH, RM ;

ZILLER, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (05) :1845-1854

[9] NICKEL-PROMOTED INTRAMOLECULAR CYCLIZATION OF VINYL BROMIDES WITH ALKENES AND ALKYNES [J].

LLEBARIA, A ;

CAMPS, F ;

MORETO, J .

TETRAHEDRON LETTERS, 1992, 33 (25) :3683-3686

[10] STUDIES ON THE COMPETITIVE NICKEL-PROMOTED CARBONYLATIVE INTRAMOLECULAR CYCLIZATION OF VINYL AND ARYL HALIDES WITH HYDROXYALKENES [J].

LLEBARIA, A ;

DELGADO, A ;

CAMPS, F ;

MORETO, JM .

ORGANOMETALLICS, 1993, 12 (07) :2825-2831