Adamantanethione and diazomethane : dual regiochemistry of cycloadditions [1]

• Autorzy: Huisgen R. , Mlostoń G.
• Języki publikacji: EN

Abstrakty

EN

Cycloadditions of diazoalkanes to thiones take place in two directions furnishing 1,3,4-thiadiazolines and/or their 1,2,3-isomers, depending upon the substituents. Adamantanethione and diazomethane give rise to both regioisomers; a literature report on the high solvent dependence of the isomer ratio is confirmed, and the two regioisomers are isolated. The 1,3,4-thiadiazoline 20 eliminates N2 at 800C(t1/2 55s) in a 1,3-dipolar cycloreversion; the thiocarbonyl ylide 22 generated undergoes electrocyclization, forming a thiirane, or is intercepted by reactions with HX (thiols, alcohols) or dipolarophilic multiple bonds. The N2 extrusion from the isomeric 1,2,3-thiadiazoline 21 is at 800C 600 times slower; the formation of the spirothiirane and homoadaadamantane-2-thione is explained by a diazonium thiolate as an intermediate.

Słowa kluczowe

EN

thioketones; diazoalkanes; thiadiazolines; 1,3-dipolar cycloadditions; thiocarbonyl ylides; ATM networks

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 1999
• Tom: vol. 73 nr 4
• Strony: 635--644

Twórcy

autor

Huisgen R.

autor

Mlostoń G.