Department of Chemistry, Stanford University , 333 Campus Drive, Stanford, California 94305, United States.
Org Lett. 2017 May 19;19(10):2630-2633. doi: 10.1021/acs.orglett.7b00961. Epub 2017 May 3.
A vanadium catalyzed 1,3-rearrangement of allenols to form transient vanadium enolates that selectively couple with electrophilic nitrogen sources is reported even in the presence of competing simple protonation and Alder-ene pathways. Hydrazine products can be cyclized in a 6-endo-trig fashion which, upon reductive cleavage of the N-N bond, yield 1,4-diamines. Additionally, cleavage of the N-N bond before cyclization can be achieved to form β-hydroxy amines, a common structural motif of biologically active compounds.
报道了一种钒催化的烯醇 1,3-重排反应，形成瞬态钒烯醇盐，它可选择性地与亲电氮源偶联，即使在存在竞争的简单质子化和 Alder-ene 途径的情况下也是如此。腙产物可以以 6-endo-trig 方式环化，然后通过还原裂解 N-N 键，生成 1,4-二胺。此外，在环化之前裂解 N-N 键也可以实现，形成β-羟基胺，这是生物活性化合物的常见结构基序。
