Titanium(IV) isopropoxide-catalysed reaction of alkylmagnesium halides with ethyl acetate in the presence of styrene. Non-hydride mechanism of ligand exchange in the titanacyclopropanes

被引：44

作者：

Epstein, OL ^{[1
]}

Savchenko, AI ^{[1
]}

Kulinkovich, OG ^{[1
]}

机构：

[1] Belarusian State Univ, Dept Organ Chem, Minsk 220050, BELARUS

来源：

TETRAHEDRON LETTERS | 1999年 / 40卷 / 32期

关键词：

Grignard reagents; titanium compounds; cyclopropanation; alkenes;

D O I：

10.1016/S0040-4039(99)01177-6

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The dependence of the yields of (E)-1-methyl-2-phenyl-1-cyclopropanol (3) on the structure of the organomagnesium compounds and reagents ratio in the reaction of ethyl acetate with Grignard reagents, in the presence of styrene and catalytic amounts of Ti(OPri)(4), has been investigated. Butylmagnesium bromide has been found to be the most suitable organomagnesium for the preparation of 3 by this method. The use of (CD3)(2)CHMgBr for the generation of the titanacyclopropane intermediates led to the formation of 3. This result disagreed with the hydride mechanism of the ligand exchange for 2-phenyltitanacyclopropane (4) formation. (C) 1999 Elsevier Science Ltd. All rights reserved.

引用

页码：5935 / 5938

页数：4

共 19 条

[1] STRUCTURE AND REACTIVITY OF BIS(PENTAMETHYLCYCLOPENTADIENYL)(ETHYLENE)TITANIUM(II), A SIMPLE OLEFIN ADDUCT OF TITANIUM [J].

COHEN, SA ;

AUBURN, PR ;

BERCAW, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (05) :1136-1143

[2] CATALYTIC DIASTEREOSELECTIVE SYNTHESIS OF CIS-1,2-DISUBSTITUTED CYCLOPROPANOLS FROM ESTERS USING A VICINAL DICARBANION EQUIVALENT [J].

COREY, EJ ;

RAO, SA ;

NOE, MC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (20) :9345-9346

[3] Titanium-mediated formation of 1,2-disubstituted cyclopropanols from esters and alkenes. A new approach to the synthesis of 3,11-dimethylnonacosan-2-one, a sex pheromone of the German cockroach [J].

Epstein, OL ;

Kulinkovich, OG .

TETRAHEDRON LETTERS, 1998, 39 (13) :1823-1826

[4] DIASTEREOSELECTIVE SYNTHESIS OF TRANS-1,2-DISUBSTITUTED CYCLOPROPANOLS FROM HOMOALLYL OR BIS-HOMOALLYL ESTERS VIA TANDEM INTRAMOLECULAR NUCLEOPHILIC ACYL SUBSTITUTION AND INTRAMOLECULAR CARBONYL ADDITION-REACTIONS MEDIATED BY TI(OPR-I)(4)/2 I-PRMGBR REAGENT [J].

KASATKIN, A ;

SATO, F .

TETRAHEDRON LETTERS, 1995, 36 (34) :6079-6082

[5]

KULINKOVICH OG, 1991, ZH ORG KHIM+, V27, P294

[6]

KULINKOVICH OG, 1991, ZH ORG KHIM+, V27, P1428

[7]

KULINKOVICH OG, 1993, MENDELEEV COMMUN, P230

[8]

KULINKOVICH OG, 1989, ZH ORG KHIM+, V25, P2244

[9] TITANIUM(IV) ISOPROPOXIDE-CATALYZED FORMATION OF 1-SUBSTITUTED CYCLOPROPANOLS IN THE REACTION OF ETHYLMAGNESIUM BROMIDE WITH METHYL ALKANECARBOXYLATES [J].

KULINKOVICH, OG ;

SVIRIDOV, SV ;

VASILEVSKI, DA .

SYNTHESIS-STUTTGART, 1991, (03) :234-234

[10] A new variant of the Kulinkovich hydroxycyclopropanation. Reductive coupling of carboxylic esters with terminal olefins [J].

Lee, J ;

Kim, H ;

Cha, JK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (17) :4198-4199

← 1 2 →