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

[11]

ENDERS D, 1992, SYNLETT, P837

[12] Aerobic epoxidation of olefins catalysed by square-planar cobalt(III) complexes of bis-N,N'-disubstituted oxamides and related ligands [J].

Estrada, J ;

Fernandez, I ;

Pedro, JR ;

Ottenwaelder, X ;

Ruiz, R ;

Journaux, Y .

TETRAHEDRON LETTERS, 1997, 38 (13) :2377-2380

[13]

FABRICE P, 1999, TETRAHEDRON LETT, V40, P531

[14] REACTIONS OF PERIODATE UNDER HOMOGENEOUS AND PHASE-TRANSFER CONDITIONS - EXAMPLES OF NEW OXIDATIONS OF UNUSUAL GROUPS [J].

FERRABOSCHI, P ;

AZADANI, MN ;

SANTANIELLO, E ;

TRAVE, S .

SYNTHETIC COMMUNICATIONS, 1986, 16 (01) :43-50

[15]

HARTMANN J, 1974, SYNTHESIS-STUTTGART, P888

[16] Syntheses of dialkyl and functionalized ketones via 1-(benzotriazol-1-yl)alkyl methyl thioethers [J].

Katritzky, AR ;

Oniciu, DC ;

Ghiviriga, I ;

Soti, F .

JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (07) :2110-2115

[17] CHEMISTRY OF SULFONYLMETHYL ISOCYANIDES .27. A NEW SYNTHESIS OF ALPHA,BETA-UNSATURATED KETONES - ALLYLIC ALKYLATION OF 1-ISOCYANO-1-TOSYLALKENES [J].

MOSKAL, J ;

VANLEUSEN, AM .

TETRAHEDRON LETTERS, 1984, 25 (24) :2585-2588

[18] Stereoselective umpolung reactions with metalated P-chiral cyanohydrin phosphates-enantioselective synthesis of tertiary cyanohydrins [J].

Schrader, T .

CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (08) :1273-1282

[19] GENERATION AND SYNTHETIC APPLICATIONS OF 2-LITHIO-1,3-DITHIANES [J].

SEEBACH, D ;

COREY, EJ .

JOURNAL OF ORGANIC CHEMISTRY, 1975, 40 (02) :231-237

[20]

Seebach D., 1969, Synthesis, P17, DOI DOI 10.1055/S-1969-34190

← 1 2 3 →