Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms

Allylation of nucleophiles with highly reactive electrophiles like allyl halides can be conducted without metal catalysts. Less reactive electrophiles, such as allyl esters and carbonates, usually require a transition metal catalyst to facilitate the allylation. Herein, we report a unique transition-metal-free allylation strategy with allyl ether electrophiles. Reaction of a host of allyl ethers with 2-azaallyl anions delivers valuable homoallylic amine derivatives (up to 92%), which are significant in the pharmaceutical industry. Interestingly, no deprotonative isomerization or cyclization of the products were observed. The potential synthetic utility and ease of operation is demonstrated by a gram scale telescoped preparation of a homoallylic amine. In addition, mechanistic studies provide insight into these C(sp(3))-C(sp(3)) bond-forming reactions. Allylation of nucleophiles with less reactive electrophiles, such as carbonates, usually requires a transition-metal catalyst. Here, the authors show a transition-metal-free allylation strategy with allyl ether electrophiles to form homoallylic amine derivatives in up to 92% yield.