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The Norrish type II reaction in the crystalline state: Toward a better understanding of the geometric requirements for gamma-hydrogen atom abstraction

TitleThe Norrish type II reaction in the crystalline state: Toward a better understanding of the geometric requirements for gamma-hydrogen atom abstraction
Publication TypeJournal Article
Year of Publication1999
AuthorsIhmels, H, Scheffer, JR
JournalTetrahedron
Volume55
Pagination885-907
Date PublishedJan
Type of ArticleArticle
ISBN Number0040-4020
KeywordsABSOLUTE ASYMMETRIC-SYNTHESIS, CONFORMATIONAL CONTROL, ENVIRONMENT, KETONES, METHODOLOGY, MOLECULES, PHOTOCHEMISTRY, PHOTOCYCLIZATION, SOLID-STATE, SPECTRA
Abstract

By correlating the success or failure of the Norrish type II reaction for a series of compounds in the crystalline state with geometric data derived from X-ray crystallography (the so-called Crystal Structure-Solid State Reactivity Method), the distance and angular requirements for photochemical gamma-hydrogen atom abstraction have been established. These studies indicate that abstractions are preferred when the C=O ... H-gamma, distance is close to the sum of the van der Waals radii of hydrogen and oxygen (2.72 Angstrom), and that the gamma-hydrogen atom can deviate by as much as 50-60 degrees from the plane containing the oxygen n-orbital responsible for abstraction. Because molecular conformations and interatomic distances and angles can be calculated readily by using empirical force field methods, such data permit predictions to be made concerning the outcome of hypothetical Norrish type II processes. (C) 1999 Elsevier Science Ltd. All rights reserved.

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