Transition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms.
basic_science · Level V
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- Record sourced from PubMed, PMID 34162867.
- Also identified by DOI 10.1038/s41467-021-24027-6 and PMC identifier 8222226.
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Abstract
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<sup>3</sup>)-C(sp<sup>3</sup>) bond-forming reactions.