Enantioselective oxidation of di-tert-butyl disulfide with a vanadium catalyst:: Progress toward mechanism elucidation

被引：110

作者：

Blum, SA

Bergman, RG ^{[1
]}

Ellman, JA

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[2] Univ Calif Berkeley, Ctr New Direct Organ Synthesis, Berkeley, CA 94720 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2003年 / 68卷 / 01期

关键词：

D O I：

10.1021/jo0205560

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism of the oxidation of di-tert-butyl disulfide (1) to the chiral thiosulfinate (2) by H2O2 catalyzed by bis(acetylacetonato)oxovanadium and a chiral Schiff-base ligand (3) has been investigated. Techniques included V-51 NMR spectroscopy, solvent effects on reaction enantioselectivity, and the isolation and full characterization of a 2:1 ligand-to-vanadium catalyst precursor. A model for the dramatic solvent effect on the enantioselectivity of this reaction was developed, based on the identification of a competing nonselective oxidation pathway. From this model, strategies for limiting this competing pathway were developed.

引用

收藏

页码：150 / 155

页数：6

相关论文

共 49 条

[11] BIOMIMICS OF VANADIUM BROMOPEROXIDASE - VANADIUM(V)-SCHIFF BASE-CATALYZED OXIDATION OF BROMIDE BY HYDROGEN-PEROXIDE [J].

CLAGUE, MJ ;

KEDER, NL ;

BUTLER, A .

INORGANIC CHEMISTRY, 1993, 32 (22) :4754-4761

[12] ON THE MECHANISM OF CIS-DIOXOVANADIUM(V)-CATALYZED OXIDATION OF BROMIDE BY HYDROGEN-PEROXIDE - EVIDENCE FOR A REACTIVE, BINUCLEAR VANADIUM(V) PEROXO COMPLEX [J].

CLAGUE, MJ ;

BUTLER, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (12) :3475-3484

[13] Asymmetric synthesis of α,α-dibranched amines by the trimethylaluminum-mediated 1,2-addition of organolithiums to tert-butanesulfinyl ketimines [J].

Cogan, DA ;

Ellman, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (01) :268-269

[14] Catalytic asymmetric oxidation of tert-butyl disulfide.: Synthesis of tert-butanesulfinamides, tert-butyl sulfoxides, and tert-butanesulfinimines [J].

Cogan, DA ;

Liu, GC ;

Kim, KJ ;

Backes, BJ ;

Ellman, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (32) :8011-8019

[15] Functional models for vanadium haloperoxidase: Reactivity and mechanism of halide oxidation [J].

Colpas, GJ ;

Hamstra, BJ ;

Kampf, JW ;

Pecoraro, VL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (14) :3469-3478

[16] Peroxovanadium complexes as radical oxidants in organic solvents and in aqueous solutions [J].

Conte, V ;

DiFuria, F ;

Moro, S .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1997, 117 (1-3) :139-149

[17] Aziridine 2-carboxylate ester mediated asymmetric synthesis of alpha-alkyl beta-amino acids [J].

Davis, FA ;

Reddy, GV ;

Liang, CH .

TETRAHEDRON LETTERS, 1997, 38 (29) :5139-5142

[18] ASYMMETRIC-SYNTHESIS AND REACTIONS OF CIS-N-(P-TOLUENESULFINYL)AZIRIDINE-2-CARBOXYLIC ACIDS [J].

DAVIS, FA ;

ZHOU, P ;

REDDY, GV .

JOURNAL OF ORGANIC CHEMISTRY, 1994, 59 (12) :3243-3245

[19]

Davis FA, 1998, CHEM SOC REV, V27, P13

[20] N-tert-Butanesulfinyl imines:: Versatile intermediates for the asymmetric synthesis of amines [J].

Ellman, JA ;

Owens, TD ;

Tang, TP .

ACCOUNTS OF CHEMICAL RESEARCH, 2002, 35 (11) :984-995

← 1 2 3 4 5 →