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.

Unique in its focus on preparative impact rather than mechanistic details, this handbook provides an overview of photochemical reactions classed according to the structural feature that is built in the photochemical step, so as to facilitate use by synthetic chemists unfamiliar with this topic. An introductory section covers practical questions on how to run a photochemical reaction, while all classes of the most important photocatalytic reactions are also included. Perfect for organic synthetic chemists in academia and industry.

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.

With contributions from 24 international authorities, Synthetic Organic Photochemistry offers a leading-edge presentation of the most recent and in-demand applications of photochemical methodologies. Outlining a wide assortment of reaction types entailing cycloadditions, cyclizations, isomerizations, rearrangements, and other organic syntheses, thi

Examines the latest applications of photochemistry to generate important intermediates Presenting the latest breakthroughs in the field of organic photochemistry, this book offers tested and proven photochemical approaches to synthesis, creating promising new possibilities and applications for photochemical reactions. It focuses on photoreactions involving an intermediate where mechanistic aspects control the course of the reaction and its synthetic value. Readers will discover new insights into the mechanisms and nature of photo-produced reactive intermediates for organic synthesis as well as the methods to generate them. Moreover, by focusing on highly efficient techniques for producing such species, the authors enable researchers to design and perform photoreactions within the framework of green, sustainable chemistry. Photochemically-Generated Intermediates in Synthesis begins with a discussion of the principles and practice of photo-generated intermediates. Next, the book explores: Photogeneration of carbon-centered radicals Photogeneration of heteroatom-centered radicals Photogeneration of biradicals and radical pairs Photochemical generation of radical ions Photogeneration of carbocations and carbanions Photogeneration of carbenes and nitrenes The book's final chapter is dedicated to the photochemical manipulation of intermediates. Each chapter includes key kinetic data for typical intermediates as well as detailed case examples, giving readers all the tools needed to perform their own photochemical reactions. Comparisons to non-photochemical methods are offered whenever possible. Photochemically-Generated Intermediates in Synthesis sets the stage for greater collaboration among photochemists and synthetic organic chemists, enabling these two research communities to fully leverage photochemistry in order to generate key intermediates needed for a broad range of synthetic reactions in organic chemistry.

An updated overview of the rapidly developing field of green techniques for organic synthesis and medicinal chemistry Green chemistry remains a high priority in modern organic synthesis and pharmaceutical R&D, with important environmental and economic implications. This book presents comprehensive coverage of green chemistry techniques for organic and medicinal chemistry applications, summarizing the available new technologies, analyzing each technique’s features and green chemistry characteristics, and providing examples to demonstrate applications for green organic synthesis and medicinal chemistry. The extensively revised edition of Green Techniques for Organic Synthesis and Medicinal Chemistry includes 7 entirely new chapters on topics including green chemistry and innovation, green chemistry metrics, green chemistry and biological drugs, and the business case for green chemistry in the generic pharmaceutical industry. It is divided into 4 parts. The first part introduces readers to the concepts of green chemistry and green engineering, global environmental regulations, green analytical chemistry, green solvents, and green chemistry metrics. The other three sections cover green catalysis, green synthetic techniques, and green techniques and strategies in the pharmaceutical industry. Includes more than 30% new and updated material—plus seven brand new chapters Edited by highly regarded experts in the field (Berkeley Cue is one of the fathers of Green Chemistry in Pharma) with backgrounds in academia and industry Brings together a team of international authors from academia, industry, government agencies, and consultancies (including John Warner, one of the founders of the field of Green Chemistry) Green Techniques for Organic Synthesis and Medicinal Chemistry, Second Edition is an essential resource on green chemistry technologies for academic researchers, R&D professionals, and students working in organic chemistry and medicinal chemistry.

This is the most updated, comprehensive collection of monographs on all aspects of photochemistry and photophysics related to natural and synthetic, inorganic, organic, and biological supramolecular systems. Supramolecular Photochemistry: Controlling Photochemical Processes addresses reactions in crystals, organized assemblies, monolayers, zeolites, clays, silica, micelles, polymers, dendrimers, organic hosts, supramolecular structures, organic glass, proteins and DNA, and applications of photosystems in confined media. This landmark publication describes the past, present, and future of this growing interdisciplinary area.