William von Eggers Doering’s Many Research Achievements during the First 65 Years of his Career in Chemistry

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• 作者：Frank-Gerrit Klrner ; Maitland Jones ; ; Ronald M. Magid
• 刊名：Accounts of Chemical Research
• 出版年：2009
• 出版时间：January 20, 2009
• 年：2009
• 卷：42
• 期：1
• 页码：169-181
• 全文大小：542K
• 年卷期：v.42,no.1(January 20, 2009)
• ISSN：1520-4898

文摘

This Account highlights William von Eggers Doering’s important discoveries in many fields of chemistry. His synthetic and mechanistic studies have contributed to areas including non-benzenoid aromatics, carbenes, pericyclic reactions, and diradical intermediates. Doering’s synthesis with L. H. Knox of the highly stable tropylium ion and their investigation of its reactivity were the starting point for the development of the field of non-benzenoid aromatics. Working with A. K. Hoffmann, Doering demonstrated the synthesis of dichloro- and dibromocarbene by base-induced α elimination of HCl or HBr from CHCl₃ or CHBr₃ under anhydrous conditions. These results allowed for the synthesis of a variety of cyclopropanes and derivatives including allenes. Using ¹⁴C labeling experiments, Doering and Prinzbach showed that the mechanism of insertion of singlet methylene into a C−H bond was a concerted process.

In their work on the Cope rearrangement, Doering and Roth’s outstanding stereochemical analysis showed that the rearrangement of acyclic 1,5-hexadienes proceeds concertedly, passing over a chairlike transition state. This work has had an enormous impact on the understanding of stereochemical control in synthetic organic chemistry, and many fruitful applications in synthesis have stemmed directly from this finding. Transition-state resonance structures analogous to those for ground-state aromatics can qualitatively explain the relatively large substituent effects on the rate of the Cope rearrangement. However, quantum chemical calculations have quantitatively described these effects. The rapid degenerate Cope rearrangements in the cis-divinylcyclopropane units of 3,4-homotropilidene, barbaralone, and bullvalene establish these molecules as having fluxional structures. The unique molecule bullvalene has more than 1.2 million possible structures interconnected by degenerate Cope rearrangements, which average all H and all C atoms. Doering has also examined stepwise thermal reorganizations that pass through intermediary 1,3- or 1,4-diradicals and do not show conformational equilibration as would be expected for classical intermediates. Doering calls these processes “not-obviously concerted”. He discusses “continuous diradicals” as transition states and rationalizes the course of these reactions through the concept of a “caldera” (a flat surface with small energy wells as found on the top of volcanoes).

The understanding of fundamental chemical reactions remains the focus of Doering’s research. In his terms, “understanding” means not only gaining deep insight but also the intellectual control that allows researchers to predict a reaction’s course. Because the interplay between theory and experiment has led to great progress in this predictive ability, Doering’s experimental work has provided an important input for computational chemistry and to the essential understanding of chemical reactions.