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Kurt M. Mislow (1923–2017)

2018; Wiley; Volume: 57; Issue: 18 Linguagem: Inglês

10.1002/anie.201800131

1521-3773

Jay S. Siegel,

Synthesis and Properties of Aromatic Compounds

Kurt M. Mislow, Hugh Stott Taylor Professor of Chemistry Emeritus at Princeton University, died peacefully on October 5th, 2017 at the age of 94. Through the use of non-numerical mathematical models to conceptualize molecular form and function, Mislow pioneered the development of a modern stereochemistry, with contributions including the chiroptical properties of biaryls, resolution of phosphine oxides, and the use of NMR spectroscopy for the study of stereodynamic processes. Mislow was born in Berlin on June 5, 1923. With the rise of National Socialism his family moved from Düsseldorf to Milan, and then to London in 1938, and a brief internment on the Isle of Man. In September 1940, just as he was about to enter the University of Cambridge, a crucial affidavit arrived from his uncle, the well-known photographer Alfred Eisenstaedt, which allowed his family to emigrate to America. Mislow graduated from Tulane University (BS; 1944) and earned his PhD degree at the California Institute of Technology under the direction of Linus Pauling in 1947. He directly joined the faculty of New York University and, in 1964, he was recruited to Princeton University. Early in his career, Mislow's deep understanding of structure–energy relationships let him to predict correctly that steric exclusion and ring strain could preclude the existence of the parent [10]- and [14]annulenes, and greatly reduce the stability of [18]annulene. This understanding of how molecules fill space empowered Mislow to explain atropisomerism in chiral biaryls and to develop a theory for their chiroptical properties and configurational stability. The connection between internal molecular mobility and the creation of isomers form a “red thread” throughout his career. Chirality and symmetry played key roles in Mislow's creation of a precise depiction of how the nanoscopic world of molecular observables correlates to the abstract model. He cared deeply about the epistemological issues that distinguished geometric models of molecules, known to be chiral by reasons of symmetry, and the molecules themselves, which depended upon reference to chiroptical observables to establish their chirality. In 1954, he discussed the possibility for a molecule with only chiral forms to be achiral (unresolvable) because of its dynamic symmetry. To address restricted atomic inversion at phosphorous, Mislow developed the first methods for the resolution of phosphine oxides and their subsequent reduction to chiral phosphines. Indeed, many of industry's most important chiral catalysts can be traced back to Mislow's designs. The advent of NMR spectroscopy made available a technique that was exquisitely sensitive to molecular symmetry. Internal and external symmetry relations could be observed and dynamics among tautomers captured in situ. Mislow capitalized on this spectroscopy to study a broad range of stereodynamic processes, and crafted a modern lexicon to articulate the complexity of these stereotopic relationships. Not only did he enable the language needed to animate these concepts eloquently, he designed and synthesized the complex molecules that embodied these concepts. Mislow saw the power of graph theory to abstract not only atoms and their bonding connectivities, but also isomers and their dynamic networks. This analysis led to the concepts of residual diastereomerism. Group theory and permutation theory sit at the core of Mislow's clarification of stereochemical relationships within, as well as among, molecules. The power of these mathematical arguments obviated the need to restrict stereochemistry to a discussion of stereoisomerism. Mislow's insight revealed the failings of the CIP basis for discussing chirality by unmasking their erroneous superposition of permutation and symmetry theory. As an emeritus professor, Mislow expanded his profound analysis from small molecules in order to develop a hierarchical topological taxonomy of complex biological and macromolecular structures. Additionally, he developed principles for specifying chirality in molecular knots that are found in DNA. Mislow was more than a great scientific scholar, he was also a towering humanist with broad and probing interests from philosophy, history, neuroscience, literature, and music. He was keenly interested in the interplay between social and public policies and the scientific enterprise. Recognition that harm and good lie in the application of knowledge, beyond the intentions of its pursuers, made him vigilant about the potential consequences of his work and how private and governmental interests impinge on contemporary research. Kurt Mislow is survived by his beloved wife of 50 years, Dr. Jacqueline Mislow. He was predeceased by their son John, a neurosurgeon. He is also survived by John's two sons, Max and John, and by Christopher Mislow, an attorney and his son from a previous marriage.