Circular Dichroism. Principles and Applications VCH. Koji Nakanishi, Nina Berova, and Robert W. Woody EDITED BY

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1 Circular Dichroism Principles and Applications EDITED BY Koji Nakanishi, Nina Berova, and Robert W. Woody VCH

Contents Contributors xv Chapter 1 Circular Dichroism: An Introduction 1 Günther Snatzke 1.1 Introduction 1 1.2 Principles of UV Spectroscopy 24 1.

2 Contents Contributors xv Chapter 1 Circular Dichroism: An Introduction 1 Günther Snatzke 1.1 Introduction Principles of UV Spectroscopy Principles of CD Spectroscopy 31 Chapter 2 From Pasteur to Parity Nonconservation: Theories of the Origin of Molecular Chirality 39 Stephen F. Mason 2.1 Introduction Pasteur on Molecular and Cosmic Dissymmetry Stereoselective Chiral Synthesis Symmetry Principles and Chiral Fields Chance and Necessity in the Evolution of Biochemical Homochirality Parity and its Nonconservation Summary and Conclusion 53 ix

CONTENTS Chapter 3 Theoretical Approach to Natural Electronic Optical Activity 59 Andrey Volosov and Robert W. Woody 3.1 From Classical Consideration to Quantum-Mechanical Models: Basic Ideas 60 3.

3 CONTENTS Chapter 3 Theoretical Approach to Natural Electronic Optical Activity 59 Andrey Volosov and Robert W. Woody 3.1 From Classical Consideration to Quantum-Mechanical Models: Basic Ideas Different Approaches to Calculation of Optical Activity What Is Practically Important in Calculation of Optical Activity Short Review of Methods Limitations of Practical Approach and Possible Directions of Development 80 Chapter 4 Circular Dichroism of Oriented Molecules 85 Hans-Georg Kuball and Alfred Schönhofer 4.1 The ACD Method Description of Polarized Spectroscopy Results and Discussion Chromophores Effect of Exciton Coupling Outlook 100 Chapter 5 Application of CD to the Study of Some Cholesteric Mesophases 105 Giovanni Gottarelli and Gian Piero Spada 5.1 Validity of CD Measurements on Cholesteric Samples CD Studies of Some Lyotropic Cholesterics 108 Chapter 6 Circularly Polarized Luminescence: A Probe for Chirality in the Excited State 121 Harry P.J.M. Dekkers 6.1 Introduction Scope of the CPL Technique Principles of Measurement and Instrumentation Relationship of Experimental and Theoretical Quantities Applications of CPL Spectroscopy: Organic Carbonyl Compounds Conclusion and Prospects 149

CONTENTS xi Chapter 7 Chiroptical Luminescence Spectroscopy as a Probe of Electronic Excited-State Structure and Dynamics in Dissymmetric Metal Complexes 153 F. S. Richardson and David H. Metcalf 7.

4 CONTENTS xi Chapter 7 Chiroptical Luminescence Spectroscopy as a Probe of Electronic Excited-State Structure and Dynamics in Dissymmetric Metal Complexes 153 F. S. Richardson and David H. Metcalf 7.1 Chiroptical Luminescence Measurements Excited-State Racemization Kinetics Circularly Polarized Excitation Spectra Enantioselective Excited-State Quenching Conclusion 176 Chapter 8 Vibrational Raman Optical Activity: From Fundamentals to Biochemical Applications 179 Laurence D. Barron and Lutz Hecht 8.1 Introduction Basic Theory of ROA ROA Instrumentation Recent Experimental ROA Studies 201 Chapter 9 Circular Dichroism of Inorganic Complexes: Interpretation and Applications 217 Reiko Kuroda and Yoshihiko Saito 9.1 Introduction Tris-Bidentate Complexes Cis-bis-Bidentate Complexes Complexes Involving Multidentate Ligands Other Complexes: fac(d)-[co (a) (BC) (DDD)] Exciton Circular Dichroism Chiral Tetrahedral Complexes Concluding Remarks 251 Chapter 10 The Octant Rule 259 David A. Lightner 10.1 Introduction Description of the Octant Rule Definition of the Octant Rule Qualitative Completeness and the Octant Rule Applications of the Octant Rule Concluding Comments 296

xii CONTENTS Chapter 11 Diene Chirality 301 J. K. Gawronski and H. M. Walborsky 11.1 Introduction 301 11.2 Skewed s-cis Dienes 306 11.3 The 1,3-Cyclohexadiene Chirality Model 313 11.

5 xii CONTENTS Chapter 11 Diene Chirality 301 J. K. Gawronski and H. M. Walborsky 11.1 Introduction Skewed s-cis Dienes The 1,3-Cyclohexadiene Chirality Model Endocyclic s-trans Dienes Exocyclic s-trans Dienes Strained Dienes (Dienes with Large Skew Angle) Interactions with Other Chromophores 326 Chapter 12 Circular Dichroism of Twisted u-electron Systems: Theoretical Determination of the Absolute Stereochemistry of Natural Products and Chiral Synthetic Organic Compounds 335 Nobuyuki Harada 12.1 Theoretical Calculation of CD and UV Spectra by the TT-Electron SCF-CI-DV MO Method Absolute Stereochemistry of (+)-l,8a-dihydro-3,8- Dimethylazulene, a Labile Biosynthetic Intermediate for 1,4-Dimethylazulene Circular Dichroism and Absolute Stereochemistry of Chiral Troponoid Spiro Compounds Absolute Stereochemistry of the Halenaquinol Family: Marine Natural Products with a Novel Pentacyclic Skeleton, as Determined by the Theoretical Calculation of CD Spectra Chiral Spiroaromatics of 9,9'-Spirobifluorene Skeleton 355 Chapter 13 The Exciton Chirality Method 361 Koji Nakanishi and Nina Berova 13.1 Exciton Coupling between Chromophores Exciton Coupling between Two Different Chromophores Additivity Relations in Exciton-Coupled CD Curves Carbohydrate Analysis Red-Shifted Chromophores 374

CONTENTS xiii 13.6 Schiff Base Chromophores for Use in the Exciton Chirality Method 379 13.7 Acyclic Polyols: Introduction 380 13.8 Acyclic 1,2-Polyols 382 13.9 Acyclic 1,2-Polyols: Anthroate//?

6 CONTENTS xiii 13.6 Schiff Base Chromophores for Use in the Exciton Chirality Method Acyclic Polyols: Introduction Acyclic 1,2-Polyols Acyclic 1,2-Polyols: Anthroate//?-Methoxycinnamate Coupling Acyclic 1,2-Polyols: Reference Curves of 1,2,3-, 1,2,3,4-, and 1,2,3,4,5-Polyol Bichromophoric Derivatives Acyclic 1,2-Amino Polyols 391 Chapter 14 S-Substituted Aromatics and Exciton Chirality 399 Chantal Andraud, Chantal Garcia, and Andre Collet 14.1 Introduction Synthesis, Optical Resolution, and Absolute Configuration of Sulfur-Substituted Cyclotriveratrylenes The Exciton Mechanism in C3- Cyclotriveratrylenes Sulfur-Substituted Cyclotriveratrylenes and Exciton Chirality Conclusion 410 Chapter 15 Circular Dichroism of the Benzene Chromophore 413 Howard E. Smith 15.1 Historical Perspective Chiroptical Observations Correlation Rules Correlation Rule Applications 426 Chapter 16 Conformational Analysis of Planar Chromophores with an Attached Chiral Rotor by CD Spectroscopy 443 Jan Sandström 16.1 Introduction Experimental and Computational Methods Results and Discussion 454

xiv CONTENTS Chapter 17 Circular Dichroism of Peptides and Proteins 473 Robert W. Woody 17.1 Peptide Backbone 474 17.2 Aromatic Side Chains and Disulfides 483 17.

7 xiv CONTENTS Chapter 17 Circular Dichroism of Peptides and Proteins 473 Robert W. Woody 17.1 Peptide Backbone Aromatic Side Chains and Disulfides Extrinsic Chromophores 488 Chapter 18 Vibrational Circular Dichroism Spectroscopy of Peptides and Proteins 497 Timothy A. Keiderling 18.1 Introduction Experimental Techniques Peptide VCD Studies Protein VCD Spectral Results Quantitative Protein VCD Studies in Terms of Structure Conclusion 516 Chapter 19 CD of Nucleic Acids 523 W. Curtis Johnson 19.1 Introduction Right-Handed Nucleic Acids Left-Handed DNA Applications of CD to Study Secondary Structure 535 Chapter 20 Circular Dichroism Coupled with HPLC: A Powerful Tool for Analytical, Stereochemical, and Spectroscopic Determinations 541 Piero Salvadori, Carlo Bertucci, and Carlo Rosini 20.1 Introduction CD Determinations of Chromatographie Elution Orders Analytical Applications of the CD Detection System in HPLC The Measurement of Circular Dichroism on Line Conclusions and Perspectives 558 Index 561

WILEY-VCH A JOHN WILEY & SONS, INC., PUBLICATION New York Chichester Weinheim Brisbane Singapore Toronto

CIRCULAR DICHROISM Principles and Applications SECOND EDITION Edited by NINA BEROVA KOJI NAKANISHI ROBERT W. WOODY WILEY-VCH A JOHN WILEY & SONS, INC., PUBLICATION New York Chichester Weinheim Brisbane