Nucleophilic benzoylation using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion.: Oxidative decarboxylation of α-hydroxyacids

被引：20

作者：

Blay, G ^{[1
]}

Fernández, I ^{[1
]}

Formentin, P ^{[1
]}

Monje, B ^{[1
]}

Pedro, JR ^{[1
]}

Ruiz, R ^{[1
]}

机构：

[1] Univ Valencia, Fac Quim, Dept Quim Organ, E-46100 Burjassot, Valencia, Spain

来源：

TETRAHEDRON | 2001年 / 57卷 / 06期

关键词：

decarboxylation; catalysts; Umpolung; cobalt; complexes;

D O I：

10.1016/S0040-4020(00)01097-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis of alkyl aryl ketones using lithiated methyl mandelate as a synthetic equivalent of the benzoyl carbanion is reported (Umpolung). The methodology involves alkylation of methyl mandelate, hydrolysis of the ester group and oxidative decarboxylation of the resulting -alpha -hydroxyacids. The last step is carried out in a catalytic aerobic way using a Co(III) complex in the presence of pivalaldehyde under very mild and advantageous conditions. The procedure is also applied to methyl mandelates substituted on the aromatic ring. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：1075 / 1081

页数：7

共 23 条

[1]

Aitken RA, 1997, SYNLETT, P293

[2]

Aitken RA, 1998, SYNLETT, P102

[3] 4-Isopropyl-2-oxazoein-5-one anion as masked umpoled synthon for both formyl and hydroxycarbonyl anions: Generation, reactivity and synthetic applications [J].

Barco, A ;

Benetti, S ;

DeRisi, C ;

Pollini, GP ;

Spalluto, G ;

Zanirato, V .

TETRAHEDRON, 1996, 52 (13) :4719-4734

[4]

BEEBE TR, 1996, J ORG CHEM, V60, P6602

[5] Catalytic aerobic oxidative decarboxylation of α-hydroxy-acids.: Methyl mandelate as a benzoyl anion equivalent [J].

Blay, G ;

Fernández, B ;

Formentin, P ;

Pedro, JR ;

Roselló, AL ;

Ruiz, R ;

Journaux, Y .

TETRAHEDRON LETTERS, 1998, 39 (20) :3327-3330

[6] REGIOSELECTIVE INTRAMOLECULAR BASE-INDUCED SYNTHESIS OF ALPHA,BETA-UNSATURATED ACYLDECALINS FROM DECALONES VIA CARBON HOMOLOGATION WITH TOSMIC - SYNTHESIS OF (+/-)-6-EUDESMEN-4-ALPHA-OL AND (+/-)-VETISELINENE [J].

BLAY, G ;

SCHRIJVERS, R ;

WIJNBERG, JBPA ;

DEGROOT, A .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (07) :2188-2194

[7] SILICON-CONTAINING CARBANIONS .1. SYNTHESIS OF VINYL THIOETHERS AND VINYLPHOSPHONATES VIA SILICON-MODIFIED ORGANOLITHIUM REAGENTS [J].

CAREY, FA ;

COURT, AS .

JOURNAL OF ORGANIC CHEMISTRY, 1972, 37 (07) :939-&

[8] ALKOXY ENEDIOLATES [J].

CIOCHETTO, LJ ;

BERGBREITER, DE ;

NEWCOMB, M .

JOURNAL OF ORGANIC CHEMISTRY, 1977, 42 (17) :2948-2950

[9] PHENYLTHIOMETHYLLITHIUM AND BIS(PHENYLTHIO)METHYLLITHIUM [J].

COREY, EJ ;

SEEBACH, D .

JOURNAL OF ORGANIC CHEMISTRY, 1966, 31 (12) :4097-&

[10]

Enders D, 1996, SYNTHESIS-STUTTGART, P48

← 1 2 3 →