Yoshihisa Inoue - Chiral Photochemistry (Molecular and Supramolecular Photochemistry)

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Chiral Photochemistry

Series Editors

V.RAMAMURTHY

Professor
Department of Chemistry
Tulane University
New Orleans, Louisiana

KIRK S.SCHANZE

Professor
Department of Chemistry
University of Florida
Gainesville, Florida

1. Organic Photochemistry, edited by V.Ramamurthy and Kirk S.Schanze

2. Organic and Inorganic Photochemistry, edited by V.Ramamurthy and Kirk S.Schanze

3. Organic Molecular Photochemistry, edited by V.Ramamurthy and Kirk S.Schanze

4. Multimetallic and Macromolecular Inorganic Photochemistry, edited by V.Ramamurthy and Kirk S.Schanze

5. Solid State and Surface Photochemistry, edited by V.Ramamurthy and Kirk S.Schanze

6. Organic, Physical, and Materials Photochemistry, edited by V.Ramamurthy and Kirk S.Schanze

7. Optical Sensors and Switches, edited by V.Ramamurthy and Kirk S.Schanze

8. Understanding and Manipulating Excited-State Processes, edited by V.Ramamurthy and Kirk S.Schanze

9. Photochemistry of Organic Molecules in Isotropic and Anisotropic Media, edited by V.Ramamurthy and Kirk S.Schanze

10. Semiconductor Photochemistry and Photophysics, edited by V.Ramamurthy and Kirk S.Schanze

11. Chiral Photochemistry, edited by Yoshihisa Inoue and V.Ramamurthy

12. Synthetic Organic Photochemistry, edited by Axel G.Griesbeck and Jochen Mattay

ADDITIONAL VOLUMES IN PREPARATION

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edited by

Yoshihisa Inoue

Osaka University
Suita, and
Japan Science and Technology Agency
Kawaguchi, Japan

V.Ramamurthy

Tulane University
New Orleans, Louisiana, U.S.A.

MARCEL DEKKER

NEW YORK

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Control of molecular chirality is central to contemporary chemistry- and biology-related areas, such as pharmaceutical, medicinal, agricultural, environmental, and materials science and technology. Thus, a wide variety of sophisticated chiral reagents, auxiliary, catalysts, hosts, and methodologies have been developed particularly in recent years as tools for controlling chiral reactions, equilibria, and recognition in both chemistry and biology.

Traditionally, chirality control has been achieved predominantly through the ground-state interactions of substrate/guest with chiral reagent/auxiliary/catalyst/host/receptor/enzyme, which are structurally and energetically well defined and characterized in considerable detail. In sharp contrast, the possibility of chirality control in the electronically excited state has not been extensively explored experimentally or theoretically, until recently. This is simply because of the long held belief that in the excited states chiral interactions, particularly the intermolecular ones, are too weak and short-lived in general to achieve high stereochemical recognition and differentiation. However, this has turned out not to be true, and several recent works have clearly demonstrated that chirality control in the excited state is not a difficult but rather a fascinating subject to study, displaying various novel phenomena which are unexpected and unprecedented in the conventional thermal chiral chemistry occurring in the ground electronic state.

The origin of chiral photochemistry, or photochirogenesis, dates back to the late 19th Century, when le Bel (1875) and vant Hoff (1894) suggested the use of circularly polarized light for so-called absolute asymmetric synthesis (AAS). The first successful AAS was achieved by Kuhn in 1929, immediately after the discovery of circular dichroism by Cotton. Modern chiral organic photochemistry may be traced back to the work of Hammond and Cole reported in 1965; they demonstrated for the first time that chiral information could be transferred from an optically active sensitizer to a substrate upon photosensitization. In the 1970s, considerable effort was devoted to the AAS of helicene precursors by Kagans and Calvins groups, while more recently, and particularly in the