TY - JOUR

T1 - Tetrasubstituted Oxathioles and Olefines Obtained by Cycloaddition of 2-Diazo-1,3-dicarbonyl Compounds to Aliphatic Thiones

AU - Ivanov, A.V.

AU - Mlosto, G.

AU - Nikolaev, V.A.

PY - 2013

Y1 - 2013

N2 - Relatively inert diazodiketones react with aliphatic thiones in a way similar to the reaction with aromatic thioketones to produce the corresponding spirocyclic oxathioles. The most probable reaction mechanism involves cycloaddition of the dipolar diazo group to the C=S bond of thione, followed by 1,5-electrocyclization of intermediate C=S ylides. Dimethyl diazomalonate reacts in this way at 19–23°C, whereas at elevated temperatures 1,3-electrocycli-zation of C=S ylide and subsequent desulfurization of thiirane lead to tetrasubstituted olefins as final products.

AB - Relatively inert diazodiketones react with aliphatic thiones in a way similar to the reaction with aromatic thioketones to produce the corresponding spirocyclic oxathioles. The most probable reaction mechanism involves cycloaddition of the dipolar diazo group to the C=S bond of thione, followed by 1,5-electrocyclization of intermediate C=S ylides. Dimethyl diazomalonate reacts in this way at 19–23°C, whereas at elevated temperatures 1,3-electrocycli-zation of C=S ylide and subsequent desulfurization of thiirane lead to tetrasubstituted olefins as final products.

KW - diazodiketones

KW - aliphatic thiones

KW - spirocyclic oxathioles

KW - C=S ylides

KW - thiiranes

KW - 1

KW - 5- and 1

KW - 3-electrocyclizations

U2 - 10.1134/S107042801307021X

DO - 10.1134/S107042801307021X

M3 - Short survey

VL - 49

SP - 1080

EP - 1082

JO - Russian Journal of Organic Chemistry

JF - Russian Journal of Organic Chemistry

SN - 1070-4280

IS - 7

ER -