Optimization of palladium-catalyzed polyene cyclizations: suppression of competing hydride transfer from tertiary amines with Dabco and an unexpected hydride transfer from 1,4-dioxane.
[figure: see text] This paper demonstrates that both 1,2,2,6,6-pentamethylpiperidine (PMP) and 1,4-dioxane can act as hydride donors in palladium-catalyzed polyene cyclizations of 2 and 3. Studies using PMP-d3 and dioxane-d8 either incorporate a deuterium atom into the monosubstituted product or completely inhibit the hydride transfer so that the second ring closure occurs in high yield. Dabco is the best substitute for PMP.
Lau
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Department of Chemistry, University of Calgary, Calgary, Alberta, Canada T2N 1N4.
Andersen
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Keay
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