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Informationen zum Autor Professor Igor V. Alabugin, Department of Chemistry and Biochemistry, Florida State University, USA Over the last 12 years, Professor Alabugin has published a body of work dedicated to stereoelectronic effects and applied these concepts in practice to the development of new organic reactions. The wide appeal of these concepts is reflected in a large number citations for his papers on the topic (the top three papers have well over 600 citations). His expertise is in broadly defined computational and experimental organic chemistry and its applications to medicinal chemistry and materials science. Klappentext Stereoelectronic Effects illustrates the utility of stereoelectronic concepts using structure and reactivity of organic molecules* An advanced textbook that provides an up-to-date overview of the field, starting from the fundamental principles* Presents a large selection of modern examples of stereoelectronic effects in organic reactivity* Shows practical applications of stereoelectronic effects in asymmetric catalysis, photochemical processes, bioorganic chemistry and biochemistry, inorganic and organometallic reactivity, supramolecular chemistry and materials science Zusammenfassung Stereoelectronic Effects illustrates the utility of stereoelectronic concepts using structure and reactivity of organic molecules* An advanced textbook that provides an up-to-date overview of the field! starting from the fundamental principles* Presents a large selection of modern examples of stereoelectronic effects in organic reactivity* Shows practical applications of stereoelectronic effects in asymmetric catalysis! photochemical processes! bioorganic chemistry and biochemistry! inorganic and organometallic reactivity! supramolecular chemistry and materials science Inhaltsverzeichnis Acknowledgement ix Supplementory Material x 1 Introduction 1 1.1 Stereoelectronic effects - orbital interactions in control of structure and reactivity 1 1.2 Orbital interactions in theoretical chemistry 3 1.3 The birth of stereoelectronic concepts in organic chemistry 4 References 6 2 Direct Effects of Orbital Overlap on Reactivity 8 2.1 Bond formation without bond breaking: types of overlap in twöorbital interactions 9 2.1.1 Factors controlling ¿¿bond overlap 12 2.2 Bond formation coupled with bond breaking 25 2.2.1 Three¿orbital interactions: stereoelectronic reasons for the preferred trajectories of intermolecular attack at a chemical bond 25 2.3 Stereoelectronics of supramolecular interactions 29 2.3.1 FMO interactions in intermolecular complexes 29 2.3.2 Expanding the palette of supramolecular interactions: from H¿bonding to Li¿, halogen, pnictogen, chalcogen and tetrel binding 30 References 36 3 Beyond Orbital Overlap: Additional Factors Important for Orbital Interactions. Classifying Delocalizing Interactions 42 3.1 Electronic count: twöelectron, one¿electron and three¿electron bonds 43 3.2 Isovalent vs. sacrificial conjugation 48 3.3 Neutral, negative, and positive hyperconjugation 49 References 52 4 Computational and Theoretical Approaches for Studies of Stereoelectronic Effects 54 4.1 Quantifying orbital interactions 54 4.2 Localized orbitals from delocalized wavefunctions 56 References 60 5 General Stereoelectronic Trends - Donors, Acceptors, and Chameleons 62 5.1 Three types of delocalization: conjugation, hyperconjugation, and ¿¿conjugation 62 5.2 Geminal and vicinal interactions 63 5.3 Stereoelectronic main rule: antiperiplanarity 64 5.3.1 Effects of bond polarity 65 5.3.2 Polarity¿induced acceptor anisotropy 68 5.4 Scales of donor and acceptor ability of orbitals: polarization, hybridization, and orbital en...
