Zhang Yueqi, Wang Danfeng, Tong Xiaofeng
Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, China.
Chem Commun (Camb). 2021 Apr 11;57(28):3488-3491. doi: 10.1039/d1cc00368b. Epub 2021 Mar 10.
While β,γ-unsaturated carbonyl compounds have been widely used as γC- or αC-nucleophiles, their potential αC,αC-bisnucleophilic reactivity is still underdeveloped. Herein, a phosphine-catalysed (4+1) annulation of β'-acetoxy allenoate and a β,γ-unsaturated carbonyl compound is reported, wherein β'-acetoxy allenoate is the 1,4-biselectrophilic component while the β,γ-unsaturated carbonyl compound serves as an αC,αC-bisnucleophile. The process not only provides a new reaction mode of β,γ-unsaturated carbonyl compounds under mild conditions but also broadens the scope of Lewis base-catalysed annulation of acetoxy allenoate.
虽然β,γ-不饱和羰基化合物已被广泛用作γC-或αC-亲核试剂，但其潜在的αC,αC-双亲核反应活性仍未得到充分开发。在此，报道了一种膦催化的β'-乙酰氧基联烯酸酯与β,γ-不饱和羰基化合物的(4+1)环化反应，其中β'-乙酰氧基联烯酸酯是1,4-双亲电组分，而β,γ-不饱和羰基化合物作为αC,αC-双亲核试剂。该过程不仅在温和条件下提供了β,γ-不饱和羰基化合物的一种新反应模式，还拓宽了乙酰氧基联烯酸酯的路易斯碱催化环化反应的范围。
