History of the Woodward-Hoffmann Rules. The No-Mechanism Puzzle

This is Paper 2 in the 27-paper series on the history of the development of the Woodward-Hoffmann rules. Paper 2 takes the reader back to the 1950s and early 1960s, before the publication of the first Woodward-Hoffmann paper in January 1965. The scope of the pericyclic no-mechanism problem is described along with many of the key "hints" or "clues" to orbital symmetry control that were available in the literature prior to 1965. A chronology of reactions with alternating stereospecificities is provided. A second chronology of alternating theoretical hints is provided, e. g., 4n+2 versus 4n. Another chronology is provided, that of the development of frontier molecular orbital theory, with and without phases and nodes. A tabulation is provided of 36 instances in which the MOs of 1,3-butadiene were reported in the literature. A knowledge of the MOs of 1,3-butadiene, plus a knowledge of some of the alternating stereospecific reactions, could have led many chemists to the solution of the pericyclic no-mechanism problem before Woodward and Hoffmann.