Hydrative trimerization of acetylene into 2-vinyloxy-1, 3-butadiene in the KOH/DMSO system: a quantum chemical insight. Issue 9 (25th February 2015)

• Record Type: Journal Article
• Authors: Vitkovskaya, Nadezhda M.; Larionova, Elena Yu.; Skitnevskaya, Anna D.; Trofimov, Boris A.
• Is Part Of: Tetrahedron letters. Volume 56:Issue 9(2015)
• Page Start: 1063
• Page End: 1066
• Publication Date: 2015-02-25
• Subjects: Acetylene -- Hydrative trimerization -- KOH/DMSO system -- 2-Vinyloxy-1, 3-butadiene -- Quantum chemical study; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2015.01.087
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Abstract: The previously described one-pot hydrative trimerization of acetylene to give 2-vinyloxy-1, 3-butadiene in the KOH/DMSO superbase system has been studied using the MP2/6-311++G ∗∗ //B3LYP/6-31+G ∗ quantum chemical framework in which the superbase system was modeled by n DMSO·KOH complexes ( n = 1 or 5). According to the results obtained, initial formation of acetaldehyde and its ethynylation to give acetylenic alcohol occurs in the coordination sphere of the K + cation. The rate-determining step is the addition of the hydroxide ion to the acetylene molecule.