Solid-state photochemistry constitutes a promising, yet underutilized, method to construct challenging carbon-carbon bonds featured in strained and sterically-encumbered structural motifs. This dissertation describes studies on leveraging the crystalline solid-state to impart high levels of chemical control over photochemical reactions aimed at the construction of complex molecules. Specifically, the stereospecific syntheses of functionalized vicinal quaternary stereocenters and sterically-congested cyclopropanes via this methodology are detailed. The regiocontrolled addition of reverse prenyl radical fragments is also described. Chapter One presents an overview of solid-state photochemistry and the considerations which must be made in engineering such reactions. This includes a description of early studies that form the foundation for thermochemical and structural parameters for successful crystalline molecules. The application to and promise in synthetic endeavors is discussed in the form of scalability and recent total syntheses of complex molecules of interest. Chapter Two details the synthesis and solid-state photodecarbonylation of a crystalline, hexasubstituted ketone wherein the six [alpha]-substituents are unique. This ketone represents one of the most complex our group has studied to date that effectively leverages the crystalline lattice to selectively construct the synthetically-daunting vicinal quaternary stereocenter motif. This work showcases the potential this methodology holds in constructing "building block" compounds that could be employed in diversity-oriented synthesis-focused projects. Chapter Three focuses on the solid-state photodenitrogenation of a set of adamantyl-1-pyrazolines to stereospecifically synthesize sterically-congested cyclopropanes. The targeted cyclopropanes similarly feature the vicinal quaternary stereocenter motif, underscoring the promise of this approach in accessing highly-strained synthons. Additionally, these pyrazolines undergo rare, solid-state thermal denitrogenations in a highly stereospecific manner, highlighting the potential for well-engineered crystalline compounds to undergo similar reactions. Chapter Four discusses a proof-of-concept study centered on the aspect of solid-state regiocontrol. Crystalline reverse prenyl ketones were shown to effectively decarbonylate and afford the regioretentive reverse prenyl photoproducts with greater selectivity compared to the solution-phase reactions. Given the prevalence of prenyl, reverse prenyl, and other unsymmetrical allyl-type fragments in terpenes and other natural products, this approach could develop into an effective strategy-level reaction to install such moieties in a regioselective manner.

Most organic reactions have long been carried out in organic solvents without concern for their real necessity, reaction efficiency, and pollution problems. Very recently, we have found that most organic reactions can be carried out in the absence of a solvent, namely, in the solid state. In many cases, the solid-state reaction proceeds more easily and efficiently, and even more selectively than solution reaction. This shows that molecules move easily and selectively in the solid state. This finding changed the classical idea which suggests "molecules do not move and reactions do not occur in the solid state", and opened up a new research field for the study molecular dynamics in the solid state. The organic solid state reactions have many possibilities to be developed. For example, enantioselective reactions can easily be accomplished by carrying out the reaction in an inclusion complex crystal with an optically active host compound. Catalytic reactions also proceed in the solid state. Moreover, the solid-state reactions are more economical and ecologically sound. In the future, pollution-free synthetic procedures in the solid state will become increasingly important, not only in chemical industries but also in university laboratories.

Photochemistry of Organic Compounds: From Concepts toPractice provides a hands-on guide demonstrating the underlyingprinciples of photochemistry and, by reference to a range oforganic reaction types, its effective use in the synthesis of neworganic compounds and in various applications. The book presents a complete and methodical approach to thetopic, Working from basic principles, discussing key techniques andstudies of reactive intermediates, and illustrating syntheticphotochemical procedures. Incorporating special topics and case studies covering variousapplications of photochemistry in chemistry, environmentalsciences, biochemistry, physics, medicine, and industry. Providing extensive references to the original literature andto review articles. Concluding with a chapter on retrosynthetic photochemistry,listing key reactions to aid the reader in designing their ownsynthetic pathways. This book will be a valuable source of information andinspiration for postgraduates as well as professionals from a widerange of chemical and natural sciences.

The second edition of this best-selling handbook is bigger, more comprehensive, and now completely current. In addition to thorough updates to the discussions featured in the first edition, this edition includes 66 new chapters that reflect recent developments, new applications, and emerging areas of interest. Within the handbook's 145 critically r

This book focuses on a variety of photochemical reaction processes in the crystalline state. The crystalline state reaction is a new category of solid state reaction, in which a reaction occurs with retention of the single crystal form. The whole reaction processes were observed directly by X-ray and neutron diffractions. In this book, not only the structures of metastable intermediates, such as radicals, carbenes, and nitrenes, but also the unstable species of photochromic compounds and photo-excited structures are shown with colored figures of the molecular structures, with more than 200 figures. The book is an indispensable resource not only for organic, inorganic and physical chemists but also for graduate students, as it furnishes more than 300 references.