Catalytic reactions of α, β-conjugated carbonyl compounds have been a practical tool towards the synthesis of different useful heterocyclic compounds. Despite the numerous reactions with carbon-carbon double bond conjugated carbonyls, reactions of acetylenic carbonyls are limited. In this study, efficient dioxole synthesis was carried out via acetylenic aldehydes and butadiene formation was preferred over cyclopropene formation via acetylenic esters as different functional groups on these substrates change the product distribution. Both reaction conditions (such as solvent and temperature) and electrophilic structure of metal carbenoids alter the product distribution; acceptor (A), donor-acceptor (DA), and acceptor-acceptor (AA) functionalized diazo compounds yield different product types over different mechanisms.