Phosphine-Catalyzed Remote 1,7-Addition for Synthesis of Diene Carboxylates

A phosphine-catalyzed remote 1,7-addition of vinyl allenoates has been developed, providing a series of 1,3-dienes derivatives in high yields (up to 99%) and with good chemo-, regio-, and stereoselectivity. This reaction demonstrated that the introduction of vinyl in allenoates effectively extended reaction types of phosphine-catalyzed nucleophilic addition of allenoates, leading to concise synthesis of diene carboxylates. Notably, the enantioselective variant of this 1,7-addition can also be performed by chiral phosphine catalyst.本工作开发了一种膦催化的乙烯基联烯酸酯远程1,7-加成反应，可在高产率（最高达99%）下获得一系列1,3-二烯衍生物，且具备良好的化学选择性、区域选择性及立体选择性。该反应证实，在联烯酸酯中引入乙烯基可有效拓展膦催化联烯酸酯亲核加成的反应类型，实现二烯羧酸酯类化合物的简洁合成。值得注意的是，采用手性膦催化剂即可实现该1,7-加成反应的对映选择性变体。