OXIDATION OF ALKYNES BY DIOXIRANES

被引：47

作者：

CURCI, R ^{[1
]}

FIORENTINO, M ^{[1
]}

FUSCO, C ^{[1
]}

MELLO, R ^{[1
]}

BALLISTRERI, FP ^{[1
]}

FAILLA, S ^{[1
]}

TOMASELLI, GA ^{[1
]}

机构：

[1] UNIV CATANIA,DIPARTIMENTO SCI CHIM,I-95126 CATANIA,ITALY

来源：

TETRAHEDRON LETTERS | 1992年 / 33卷 / 51期

关键词：

DIOXIRANES; OXYGEN TRANSFER; ALKYNES; OXIDATION; OXIRENES; KETENES; ALPHA; BETA-UNSATURATED CARBONYLS;

D O I：

10.1016/S0040-4039(00)74781-2

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

In situ generated or isolated dimethyldioxirane (1a) and methyl(trifluoromethyl)dioxirane (1b) efficiently afford oxidation of alkynes, most likely via oxirene intermediates, which rearrange into ketene or alpha,beta-unsaturated carbonyls, or else are further oxidized to alpha,beta-dicarbonyls. Diphenylacetylene and phenylacetylene yield mostly ketene derived products, whereas 8-hexadecyne (an internal dialkyl alkyne) gives 9-hexadecen-8-one (both trans and cis) as the main product. Reaction of cyclodecyne (a conformationally rigid cycloalkyne) with isolated 1b affords cis-bicyclo[5.3.0]decan-2-one (15) and cis-bicyclo[4.4.0]decan-2-one (16). which derive from the oxirene by stereoselective 1.5- and 1,6-transanular insertion, respectively.

引用

页码：7929 / 7932

页数：4

共 31 条

[1] SPECTRAL AND CHEMICAL-PROPERTIES OF DIMETHYLDIOXIRANE AS DETERMINED BY EXPERIMENT AND ABINITIO CALCULATIONS [J].

ADAM, W ;

CHAN, YY ;

CREMER, D ;

GAUSS, J ;

SCHEUTZOW, D ;

SCHINDLER, M .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (13) :2800-2803

[2] PHASE-TRANSFER CATALYTIC-OXIDATION OF TERMINAL ALKYNES TO KETO ALDEHYDES BY DILUTE HYDROGEN-PEROXIDE [J].

BALLISTRERI, FP ;

FAILLA, S ;

TOMASELLI, GA .

JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (04) :830-831

[3]

BALLISTRERI FP, 1986, TETRAHEDRON LETT, V27, P1539

[4]

BASSIGNANI L, 1978, J ORG CHEM, V21, P4245

[5] O-17 AND C-13 IDENTIFICATION OF THE DIMETHYLDIOXIRANE INTERMEDIATE ARISING IN THE REACTION OF POTASSIUM CARBONATE WITH ACETONE [J].

CASSIDEI, L ;

FIORENTINO, M ;

MELLO, R ;

SCIACOVELLI, O ;

CURCI, R .

JOURNAL OF ORGANIC CHEMISTRY, 1987, 52 (04) :699-700

[6] PERACID OXIDATION OF ACETYLENES - 1,2-METHYL MIGRATION, CYCLOPROPANE FORMATION, AND STEREOSELECTIVE 1,5-TRANSANNULAR AND 1,6-TRANSANNULAR INSERTION [J].

CIABATTONI, J ;

CAMPBELL, RA ;

RENNER, CA ;

CONCANNON, PW .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1970, 92 (12) :3826-+

[7]

CICALA G, 1982, J ORG CHEM, V47, P2679

[8]

CONCANNON PW, 1972, THESIS BROWN U

[9] TRANSANNULAR REACTIONS IN MEDIUM-SIZED RINGS [J].

COPE, AC ;

MARTIN, MM ;

MCKERVEY, MA .

QUARTERLY REVIEWS, 1966, 20 (01) :119-&

[10] ASYMMETRIC EPOXIDATION OF UNFUNCTIONALIZED ALKENES BY DIOXIRANE INTERMEDIATES GENERATED FROM POTASSIUM PEROXOMONOSULPHATE AND CHIRAL KETONES [J].

CURCI, R ;

FIORENTINO, M ;

SERIO, MR .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (03) :155-156

← 1 2 3 4 →