Seeman Jeffrey I
Department of Chemistry, University of Richmond, 23173, Richmond, VA, USA.
Chem Rec. 2022 Feb;22(2):e202100212. doi: 10.1002/tcr.202100212.
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.
这是伍德沃德-霍夫曼规则发展历程系列27篇论文中的第二篇。第二篇论文带领读者回到20世纪50年代和60年代初，即1965年1月第一篇伍德沃德-霍夫曼论文发表之前。文中描述了周环无机理问题的范围，以及1965年之前文献中可用的许多关于轨道对称性控制的关键“提示”或“线索”。提供了具有交替立体专一性的反应年表。还提供了第二个交替理论提示的年表，例如4n + 2与4n。此外还提供了另一个年表，即前沿分子轨道理论的发展年表，包括有相位和节点以及无相位和节点的情况。文中列出了文献中报道1,3-丁二烯分子轨道的36个实例。了解1,3-丁二烯的分子轨道，再加上一些交替立体专一性反应的知识，可能会使许多化学家在伍德沃德和霍夫曼之前就解决周环无机理问题。
