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Selectivity in the Formal [2 + 2 + 2] Cycloaromatization of Enyne-Allenes Generated by the Alder-ene Reaction from
Duy-Viet Vo1, Tongtong Wu2, Yanshu Luo2
1Department of Chemistry, University of Illinois Chicago, 845 W. Taylor St., Chicago, Illinois 60607, United States.
Abstract:
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.
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