Noteworthy, while the Z/E ratio for linear alkyne is usually in the range of 4-6, the congested alkyne 1h achieved an exceptional ratio exceeding 20. Aromatic alkynes, including those equipped with electronically diversified aromatic units (1l-p), reacted with synthetically useful yields (40-70%). However, electron-poor and neutral arene substrates (1l-m, 1o-p) required switching to toluene as a solvent due to product decomposition observed in DCM. For alkynes with adjacent aromatic substituents, Z/E stereoselectivities surpass 20 in all cases.