Selectivity in the Formal 2 + 2 + 2 Cycloaromatization of Enyne-Allenes Generated by the Alder-ene Reaction from Triynes

1,3-Diynyl propiolates undergo the Alder-ene reaction to generate enyne-allenes, which participate in the Diels-Alder reaction to provide products of a formal [2 + 2 + 2] cycloaromatization of three alkynes. Without an external alkyne, enyne-allene reacts with one of the alkyne moieties of 1,3-diyny...

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Veröffentlicht in:Organic letters 2024-09, Vol.26 (37), p.7778
Hauptverfasser: Vo, Duy-Viet, Wu, Tongtong, Luo, Yanshu, Xia, Yuanzhi, Lee, Daesung
Format: Artikel
Sprache:eng
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Zusammenfassung:1,3-Diynyl propiolates undergo the Alder-ene reaction to generate enyne-allenes, which participate in the Diels-Alder reaction to provide products of a formal [2 + 2 + 2] cycloaromatization of three alkynes. Without an external alkyne, enyne-allene reacts with one of the alkyne moieties of 1,3-diynyl propiolate, whereas external alkynes can be used to trap enyne-allene to provide various arene products. The substituents on the dienophilic alkynes have a profound impact on their reactivity. In this Diels-Alder reaction, 1,3-diynes display higher reactivity than monoynes; thus, an excess amount (4-5 equiv) of external monoynes needs to be employed to get good product selectivity.1,3-Diynyl propiolates undergo the Alder-ene reaction to generate enyne-allenes, which participate in the Diels-Alder reaction to provide products of a formal [2 + 2 + 2] cycloaromatization of three alkynes. Without an external alkyne, enyne-allene reacts with one of the alkyne moieties of 1,3-diynyl propiolate, whereas external alkynes can be used to trap enyne-allene to provide various arene products. The substituents on the dienophilic alkynes have a profound impact on their reactivity. In this Diels-Alder reaction, 1,3-diynes display higher reactivity than monoynes; thus, an excess amount (4-5 equiv) of external monoynes needs to be employed to get good product selectivity.
ISSN:1523-7052
1523-7052
DOI:10.1021/acs.orglett.4c01649