Unexpected heterocyclization of electrophilic alkenes by tetranitromethane in the presence of triethylamine. Synthesis of 3-nitroisoxazoles.
Novel reaction of tetranitromethane (TNM) with electrophilic alkenes in the presence of triethylamine yielding substituted 3-nitroisoxazoles was found and studied. Triethylamine increases the reactivity of TNM toward electrophilic alkenes promoting their heterocyclization, and the reactions proceed in an unusual way. A variety of alpha,beta-unsaturated aldehydes, ketones, esters, amides, phosphonates, and nitro and sulfur compounds was involved in the heterocyclization reaction, and a wide range of functionalized 3-nitroisoxazoles was obtained in good to high yields. The scope and limitations of the reaction and the mechanistic aspects are discussed.
Volkova
Yulia A
YA
Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory, 1-3, Moscow 119992, Russia.
Averina
Elena B
EB
Grishin
Yuri K
YK
Bruheim
Per
P
Kuznetsova
Tamara S
TS
Zefirov
Nikolai S
NS
D000447:Aldehydes / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry*; D000577:Amides / Q000737:chemistry; D020650:Combinatorial Chemistry Techniques; D003500:Cyclization; D004952:Esters / Q000737:chemistry; D005021:Ethylamines / Q000737:chemistry*; D007555:Isoxazoles / Q000138:chemical synthesis*; D007659:Ketones / Q000737:chemistry; D015394:Molecular Structure; D009574:Nitro Compounds / Q000138:chemical synthesis*; D063065:Organophosphonates / Q000737:chemistry; D013457:Sulfur Compounds / Q000737:chemistry; D013774:Tetranitromethane / Q000737:chemistry*
D000447:Aldehydes; D000475:Alkenes; D000577:Amides; D004952:Esters; D005021:Ethylamines; D007555:Isoxazoles; D007659:Ketones; D009574:Nitro Compounds; D063065:Organophosphonates; D013457:Sulfur Compounds; D013774:Tetranitromethane; C016162:triethylamine