Acylation of a transient Ti(IV)-enolate by acyl halides and anhydrides. Facile synthesis of alpha-hydroxy-beta-ketoesters

被引：3

作者：

Clerici, A ^{[1
]}

Clerici, L ^{[1
]}

Porta, O ^{[1
]}

机构：

[1] POLITECN MILAN,DIPARTIMENTO CHIM,I-20131 MILAN,ITALY

来源：

TETRAHEDRON | 1996年 / 52卷 / 33期

关键词：

D O I：

10.1016/0040-4020(96)00621-7

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Regioselective C-acylation at the carbonyl carbon of methyl phenylglyoxylate 1 occurs by reaction with a variety of acyl halides 3 and anhydrides 4 in the presence of TiCl3/py system in THF at room temperature. alpha-Hydroxy-beta-ketoesters 5 are the only reaction products and pyridine is essential to obtain useful yields (50-90%). The mechanism of acylation involves the intermediacy of a nucleophilic a Ti(IV)-ene diolate B. Copyright (C) 1996 Elsevier Science Ltd

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页码：11037 / 11044

页数：8

相关论文

共 17 条

[1] EFFICIENT SYNTHESIS OF ALPHA-HYDROXY-BETA-KETOESTERS FROM METHYL PHENYLGLYOXALATE AND ACID-CHLORIDES MEDIATED BY TITANIUM TRICHLORIDE [J].

ARANEO, S ;

CLERICI, A ;

PORTA, O .

TETRAHEDRON LETTERS, 1994, 35 (14) :2213-2216

[2]

BECCALLI EM, 1984, GAZZ CHIM ITAL, V114, P389

[3] A TRICOMPONENT REACTION PROMOTED BY A TITANIUM TRICHLORIDE PYRIDINE SYSTEM DIASTEREOSELECTIVE SYNTHESIS OF BETA-AMINO-ALPHA-HYDROXYESTERS [J].

CLERICI, A ;

CLERICI, L ;

PORTA, O .

TETRAHEDRON LETTERS, 1995, 36 (33) :5955-5958

[4] EFFICIENT DIASTEREOSELECTIVE SYNTHESIS OF ALPHA,BETA-DIHYDROXYESTERS FROM METHYL PHENYLGLYOXYLATE AND ALDEHYDES MEDIATED BY TITANIUM TRICHLORIDE/PYRIDINE SYSTEM [J].

CLERICI, A ;

CLERICI, L ;

MALPEZZI, L ;

PORTA, O .

TETRAHEDRON, 1995, 51 (48) :13385-13400

[5] UNUSUAL OXIDATIVE CLEAVAGE OF METHYL DIPHENYLTARTRATE PROMOTED BY TITANIUM TETRACHLORIDE PYRIDINE SYSTEM [J].

CLERICI, A ;

CLERICI, L ;

PORTA, O .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (03) :480-481

[6] CATALYSIS BY ALPHA-SUBSTITUTED PYRIDINES IN THE HYDROLYSIS OF ARYL ACETATES AND ACETIC-ANHYDRIDE [J].

DEADY, LW ;

FINLAYSON, WL .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1983, 36 (10) :1951-1956

[7] ACETYLPYRIDINIUM ION INTERMEDIATE IN PYRIDINE-CATALYZED HYDROLYSIS AND ACYL TRANSFER REACTIONS OF ACETIC ANHYDRIDE - OBSERVATION, KINETICS, STRUCTURE-REACTIVITY CORRELATIONS, AND EFFECTS OF CONCENTRATED SALT SOLUTIONS [J].

FERSHT, AR ;

JENCKS, WP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1970, 92 (18) :5432-&

[8]

HORI T, 1969, J CHEM SOC CHEM COMM, P528

[9]

LEDAO H, 1974, HELV HIM ACTA, V57, P2215

[10]

MARCH J, 1985, ADV ORG CHEM, P850