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Mechanistic study on Mo(CO) 6 ‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes
Author(s) -
Meng Qingxi,
Li Ming
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1860
Subject(s) - cycloaddition , intramolecular force , chemistry , catalysis , transition state , density functional theory , medicinal chemistry , triple bond , computational chemistry , reaction conditions , photochemistry , stereochemistry , double bond , polymer chemistry , organic chemistry
By means of density functional theory, the Mo(CO) 6 ‐catalyzed intramolecular [2 + 2] or [2 + 2 + 1] cycloaddition reaction of 5‐allenyl‐1‐ynes was investigated. All the intermediates and transition states were optimized completely at B3LYP/6‐311++G(d,p) level (LANL2DZ(f) for Mo). Calculations indicate that the complexation of 5‐allenyl‐1‐ynes with Mo(CO) 6 occurred preferentially at the triple bond to give the complex M1 and then the complexation with the distal double bond of the allenes generates the complex M5 . In this reaction, Mo(CO) 6 ‐catalyzed intramolecular [2 + 2] cycloaddition is more favorable than [2 + 2 + 1] cycloaddition. The reaction pathway Mo(CO) 6 + R → M5 → T7 → M12 → M13 → T11 → M18 → P4 is the most favorable one, and the most dominant product predicted theoretically is P4 . The solvation effect is remarkable, and it decreases the reaction energy barriers. Copyright © 2011 John Wiley & Sons, Ltd.