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A facile thermal cyclization of ynamide‐tethered 1,3,8‐triynes to form a 3,5,6,7‐tetrahydro‐1H‐pyrano[3,4‐c]pyridine skeleton is described. Although the mechanism of this unusual reaction has yet to be defined, the formation of either a strained keteniminium or a biradical intermediate followed by a 1,5‐hydride or ‐hydrogen shift is tentatively proposed as the key elementary steps in the reaction...
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