Direct nitrogenation catalyzed by early transition metal complexes

研究了亲氧前过渡金属配合物对烯烃和含羟基或羰基的官能化二烯的直接氮化反应。考察了三异丙氧基钒VO（OiPr）_3催化亚硝子反应和亚硝基Diels-Alder反应的性能。用V（V）催化剂（1mol%）氧化异羟肟酸可有效地生成亚硝基羰基中间体，无其它氧化副产物。具有羰基的共轭二烯以较高的产率和区域选择性转化为亚硝基Diels-Alder加合物。

The direct nitrogenation of alkenes and functionalized dienes having hydroxy or carbonyl groups was examined by using oxophilic early transition metal complexes. The vanadium(V) oxytriisopropoxide VO(OiPr)3 has been examined as catalyst for nitroso ene reaction and nitroso Diels-Alder reaction. The nitrosocarbonyl intermediates can be efficiently generated by the oxidation of hydroxamic acids with V(V) catalyst (1mol%) without any other oxygenated by-products. The conjugated dieneshaving carbonyl group were converted to the nitroso Diels-Alder adducts in good yieldswith high regioelectivity.