On ring carbomers of cyclobutane, cyclopentane, and cyclodecane and cyclization reactions through bis(alkynyl-propargyl) coupling.

A copper-mediated procedure for terminal alkynyl-propargyl coupling has been applied to "skipped" bis-terminal undecatetrayne and 1,4-bis(pseudo)halobut-2-ynes with the aim of preparing ring carbomers of representative strained and loose cycloalkanes, namely [N]pericyclynes. Two unprecedented, cyclic. "skipped" polyynes with CH2 vertices have been isolated as mixtures of diastereoisomers: an isomer 1b and a dimer 2a of [5]pericyclyne 1a. The isomer 1b is a cyclotetrayne with an exocyclic allene function resulting from a unique formal SN process. Its structure has been established by 1H/13C HMQC and HMBC two-dimensional NMR analysis. According to density functional theory calculations, it is about 6 kcalmol(-1) more stable than [5]pericyclyne (1a). Compound 1b can also be regarded as a C13-relaxed [4]pericyclyne, a long sought "skipped" C12 tetrayne. The dimer 2a is a C30 ring that results from a formal SN process. It is a stable ring carbomer of cyclodecane, that is, a [10]pericyclyne, with four CH2 vertices.