末端アルケンを求核剤とするカルボニル化合物の触媒的アリル化反応

抄録

We herein describe a cobalt/Xantphos system enabling highly challenging catalytic nucleophilic functionalizations of low-reactive carbonyl compounds via C(sp³)-H bond cleavage. The combination of Co(acac)₂, Xantphos, and AlMe₃ was crucial to convert terminal alkenes into nucleophilic allylation reagents. With the aid of this system, CO₂ and various ketones were efficiently allylated using various allylarenes, 1,4-dienes, and simple α-olefins. The regioselectivity switched depending on the alkenes and ketones used. Furthermore, the intramolecular cyclization of ketoalkenes provided tertiary homoallylic cycloalkanols with good diastereoselectivity, leading to demonstration of a short-step synthesis of biologically active compound, tramadol.