Sleeping Beauties in Chemistry. Oosterhoff, Havinga and Schlatmann: Four Years Before “The Woodward‐Hoffmann Rules”^†**

Abstract

Several forerunners to the Woodward‐Hoffmann rules appear in the chemical literature in the early 1960s. While these precedents refer to orbital symmetry and explain either electrocyclic reactions (Luitzen Oosterhoff, cited by Egbert Havinga and Jos Schlatmann in Tetrahedron in 1961) or some cycloaddition reactions (Kenichi Fukui, in a book chapter published in 1964), they did not attract any attention and did not serve to initiate any research prior to the publication of the five Woodward and Hoffmann communications in 1965. Even Woodward and Hoffmann were unaware of these precedents (though Hoffmann knew of Fukui's frontier orbital theory) until after they had completed the relevant portions of their work. The Oosterhoff‐Havinga‐Schlatmann story will be told in this paper; the Fukui story will be told in the next paper in this series on the history of the development of the Woodward‐Hoffmann rules. Explanations for these precedents not being productive in solving the no‐mechanism problem are discussed.

Why Woodward and Hoffmann? And Why 1965?**

“…In December 1960, Dutch chemist Egbert Havinga and his graduate student Jos Schlatmann asked their colleague Luitzen Oosterhoff if he could explain a variety of perplexing stereospecific reactions in the chemistry of vitamin D (see Figure 1 for just a piece of their story). As published briefly and without enthusiasm by Havinga and Schlatmann in 1961 [34] and told in greater detail in Publication 3 in this series, [35] Oosterhoff suggested a frontier molecular orbital (FMO) explanation: orbital symmetry. He had reservations regarding his own suggestion, and that discouraged Havinga from pursuing the idea further.…”

“…He had reservations regarding his own suggestion, and that discouraged Havinga from pursuing the idea further. [35] And even though that suggestion was published in Tetrahedron in 1961, [34] no one followed up on it either.…”

My first and my latest publication

“…The No-Mechanism Reaction Puzzle [9] 3 A Sleeping Beauty in Chemistry. Oosterhoff, Havinga and Schlatmann, Four Years Before "The Woodward-Hoffmann Rules" [10] 4-Part I Kenichi Fukui, Frontier Molecular Orbital Theory, and the Woodward-Hoffmann Rules. Part I.…”

“…The early 1960s were particularly ripe for great creativity in organic chemistry! What is also fascinating about this episode in the history of chemistry is why these others who came before Woodward and Hoffmann did not see their discoveries immediately seized upon by others as were Woodward and Hoffmann's ideas [10][11][12][13] ; and why several others were so very close but did not get there. And then there are others who came after Woodward and Hoffmann and felt that their contributions were undervalued and credit misassigned.…”

“…This cartoon and many others appear in my first paper on the history of the Woodward-Hoffmann rules [1] which is herein referred to as "my latest publication" F I G U R E 3 (left to right) William G. Dauben, Michael S. Kellogg, and Wayne Spitzer, as they were in the late 1960s. Spitzer is shown reacting the paper by Junes Ipaktschi in Tetrahedron Letters [1969, (10) 2153-2156] that initiated the collaboration at Berkeley 1971 was the brilliant Michael S. Kellogg (Figure 3). Mike had been an undergraduate researcher in Howard E. Zimmerman's group at the University of Wisconsin.…”