access to 6-hydroxyl-2,8-DOBCOs. Mechanistic studies indicate that the V(V) species, generated under epoxidation conditions, promotes the ring rearrangement in a stereospecific manner. Meanwhile, the ε-hydroxyl-β,γ-unsaturated ketones are transformed into 6-amino-2,8-DOBCOs by a Cu-catalyzed cascade of aziridination and ring rearrangement. In the end, the one-pot approach toward 6-hydroxyl- or 6-amino-2
通过顺序催化实现2,8-二氧杂
双环[3.2.1]辛烷(2,8-DOBCO)
缩酮的模块化合成。关键的中间体ε-羟基-β,γ-不饱和酮很容易通过Ni催化的1,3-二烯,醛和酰基
锆茂试剂的三组分偶联而获得。这些多官能化的酮可经历V催化的环氧化和环重排的级联反应,以提供进入6-羟基-2,8-DOBCO的通道。机理研究表明,在环氧化条件下产生的V(V)物种以立体特异性方式促进环的重排。同时,通过
铜催化的
叠氮化和环重排反应,将ε-羟基-β,γ-不饱和酮转化为6-
氨基-2,8-DOBCO。最后,采用一锅法从1,3-二烯,
醛类向6-羟基-或6-
氨基-2,8-DOBCOs迁移,