Asymmetric Autocatalysis : The Soai Reaction / edited by Kenso Soai, Tsuneomi Kawasaki, and Arimasa Matsumoto.

Format:

Book

Author/Creator:

Kenso Soai

Contributor:

Soai, Kenso, editor.

Kawasaki, Tsuneomi, editor.

Matsumoto, Arimasa, editor.

Series:

ISSO (Series)

Issn Series

Language:

English

Subjects (All):

Asymmetric synthesis.

Autocatalysis.

Enantioselective catalysis.

Physical Description:

1 online resource (391 pages)

Edition:

First edition.

Place of Publication:

London, England : The Royal Society of Chemistry, [2023]

Summary:

Asymmetric Autocatalysis provides a comprehensive introduction to the topic of autocatalysis and an in-depth review of the current state of the research.

Contents:

Intro

Title

Copyright

Contents

Chapter 1 Asymmetric Autocatalysis: The Soai Reaction, an Overview

1.1 Introduction

1.1.1 Characteristic Features of Life

1.1.2 Origin of Homochirality and Amplification of Enantiomeric Excess

1.2 Asymmetric Autocatalysis

1.2.1 Principle of Asymmetric Autocatalysis

1.2.2 Discovery of Asymmetric Autocatalysis of 5-Pyrimidyl, 3-Quinolyl, and 5-Carbamoyl-3-pyridyl Alkanols with Amplification of Enantiomeric Excess: The Soai Reaction

1.2.3 Trajectory Leading to the Discovery of Asymmetric Autocatalysis

1.2.4 The First Asymmetric Autocatalysis of 3-Pyridyl Alkanol

1.2.5 Highly Enantioselective Asymmetric Autocatalysis

1.2.6 Discovery of Asymmetric Autocatalysis with Amplification of Enantiomeric Excess. The Soai Reaction

1.2.7 Investigation of the Mechanism of Asymmetric Autocatalysis

1.3 Studies on the Origins of Homochirality by Using Asymmetric Autocatalysis

1.3.1 Circularly Polarized Light

1.3.2 Chiral Inorganic Crystals of Quartz, Cinnabar, Sodium Chlorate, Retgersite, and the Enantiotopic Face of Achiral Crystals of Gypsum

1.3.3 Organic Crystals

1.4 Absolute Asymmetric Synthesis

1.4.1 Realization of Absolute Asymmetric Synthesis

1.4.2 Absolute Asymmetric Synthesis under Solid-Vapor Conditions

1.5 Chiral Hydrogen, Carbon, Oxygen, and Nitrogen Isotopomers Act as the Origin of Homochirality in Conjunction with Asymmetric Autocatalysis

1.6 Various Chiral Materials Including Cryptochiral Compounds as Triggers for Asymmetric Autocatalysis

1.7 Unusual Phenomena of the Reversal of the Sense of Enantioselectivities Detected by Asymmetric Autocatalysis

1.8 Application of Asymmetric Autocatalysis for the Synthesis of Various Chiral Compounds

1.9 Conclusions

Acknowledgements

References.

Chapter 2 Asymmetric Autocatalysis Initiated by Enantioenriched Chiral Organic Compounds: The Link Between Circularly Polarized Light and Nearly Enantiopure Organic Compounds

2.1 Introduction

2.2 Asymmetric Autocatalysis Initiated by Various Chiral Compounds

2.3 Chiral Discrimination of Cryptochiral Saturated Quaternary Hydrocarbons

2.4 Correlation Between Circularly Polarized Light and Highly Enantioenriched Organic Compounds Mediated by Asymmetric Autocatalysis

2.5 Conclusion

References

Chapter 3 Asymmetric Autocatalysis Triggered by the Chirality of Minerals, Organic Crystals, and Surfaces

3.1 Crystal Chirality of Achiral Compounds

3.2 Chirality of Minerals and Inorganic Crystals as a Trigger for Asymmetric Autocatalysis

3.2.1 SiO2 Quartz

3.2.2 Sodium Chlorate and Bromate

3.2.3 Cinnabar HgS

3.2.4 Retgersite

3.3 Chirality of Organic Compounds

3.3.1 Chiral Crystal of Organic Compounds

3.3.2 Chiral Crystal of a Complex

3.3.3 Chiral Crystal of Co-crystals

3.3.4 Chiral Crystal of Simple Organic Compounds

3.3.5 Chiral Crystal of Amino Acid Related Compounds

3.3.6 Chiral Crystal of Nucleic Acid Base Compounds

3.4 Chirality of Crystal Surfaces

3.5 Summary

Chapter 4 Absolute Asymmetric Synthesis in the Soai Reaction

4.1 Introduction

4.2 Asymmetric Autocatalysis with Amplification of Enantiomeric Excess: The Soai Reaction

4.3 Absolute Asymmetric Synthesis in The Soai Reaction

4.3.1 Absolute Asymmetric Synthesis Enabled by the Soai Reaction in Solution, in the Presence of Achiral Silica Gel and in the Presence of Achiral Amines

4.3.2 Absolute Asymmetric Synthesis by the Soai Reaction Under Solid-Vapor Conditions

4.4 Conclusions

Chapter 5 Isotope Chirality and Cosmochemistry.

5.1 Introduction

5.1.1 Carbon

5.1.2 Hydrogen

5.1.3 Nitrogen

5.1.4 Oxygen

5.2 Results and Discussion

5.3 Conclusions

Chapter 6 Reaction Mechanism in the Study of Amplifying Asymmetric Autocatalysis

6.1 Introduction

6.1.1 Scope of and Limitations to the Study of Reaction Mechanisms

6.1.2 General Features of Autocatalytic Mechanisms

6.2 The Key Steps Towards Amplifying Asymmetric Autocatalysis (AAA)

6.2.1 Catalytic Asymmetric Synthesis

6.2.2 Non-linear Effects (NLE)

6.2.3 Autocatalysis

6.2.4 Chiral Amplification Through Phase Change

6.2.5 Asymmetric Catalysis Creating Amplification Through NLE

6.2.6 Absolute Asymmetric Synthesis (AAS)

6.3 The Pathway That Led to the First Examples of AAA

6.4 The Progression of Mechanistic Understanding of the Soai Reaction

6.4.1 Background: The Catalyzed Reaction of Dialkyl Zinc with Aldehydes

6.4.2 Kinetic Approaches to the Mechanism of AAA

6.4.3 Computational Approaches to the Mechanism of AAA

6.4.4 Spectroscopic Approaches to the Mechanism of AAA

6.4.5 X-ray Crystallography for Mechanistic Insights into AAA

6.5 Current Understanding of the AAA Catalytic Cycle

6.5.1 Molecular Weights from Diffusion-ordered Spectroscopy

6.6 Phase Variation in AAA

6.7 The Sensitivity of AAA to Internal and External Factors

Chapter 7 Spontaneous Emergence of Chirality in Autocatalytic Cycle Models of the Soai Reaction

7.1 Introduction

7.2 Reductionist Frank Models of the Soai Reaction

7.2.1 Models of Rivera Islas et al.

7.2.2 Models of Crusats et al.

7.3 Mechanistic Investigations of the Soai Reaction

7.3.1 Hemiacetal and Aldehyde Involvement Within the Autocatalytic Scaffold

7.3.2 Background Uncatalyzed Racemic Alkylation

7.3.3 Varying Zinc Alkoxides and Aldehydes Structures.

7.3.4 Influence of the Isotopic Chirality

7.4 Critical Analysis of Two Specific Realistic Models: Noble-Terán vs. Trapp Cycles

7.4.1 The Noble-Terán Cycle

7.4.2 The Trapp Cycle

7.5 Conclusion

Chapter 8 Mechanism of the Soai Reaction - DFT and Kinetic Computations of the Catalytic Cycle

8.1 Introduction

8.2 Structure of the Product in Solution as a Source for Calibration of Computation Results

8.3 Comparison of the Computed Catalytic Cycles

8.3.1 DFT Mechanisms - A General Consideration

8.3.2 Dimer Catalyst Mechanism - Barrels Empty and Full

8.3.3 Tetrameric Mechanism - Brandy Party,

8.4 Kinetic Approach for Exploring the Mechanism of the Soai Reaction

8.4.1 Browsing the Known Kinetic Data

8.4.2 Simulations of the Kinetics in the Soai Reaction

8.4.3 Deterministic vs. Stochastic Kinetic Modeling

8.5 Conclusions and the Objectives of a Kinetic Description

Chapter 9 Stochastic Modeling of Asymmetric Autocatalysis in the Soai Reaction

9.1 Introduction

9.2 Fundamentals of Stochastic Kinetics

9.3 A Particle-based View on Racemates

9.4 Minimal Models of the Soai Reaction

9.5 Mechanism-based Modeling

9.6 Distribution Asymmetry

9.7 Conclusion

Chapter 10 Demystifying the Soai Reaction

10.1 Introduction

10.1.1 Biological Homochirality, Absolute Asymmetric Synthesis, and Asymmetric Autocatalysis

10.1.2 The Soai Reaction

10.1.3 Mechanistic Challenges and Prior Art

10.2 Demystifying the Evolution of the Structure and Function of the SMS Tetramer

10.2.1 Competency of a Pyridine System - One of the Nitrogen Atoms in the Pyrimidine Core is Dispensable in the Soai Reaction

10.2.2 Structure-Activity Relationships of the Pyridinyl Autocatalyst.

10.2.3 Spectroscopy of Zinc Alkoxides and the 'Cube-Escape' Model for the Assembly of the SMS Tetramer

10.2.4 Substrate Binding by the SMS Tetramer

10.2.5 Enantioselective Alkyl Transfer by the SMS Tetramer

10.2.6 The Origin of Non-linearity

10.3 Structural Contributions to Amplifying Autocatalysis in the Soai Reaction

10.3.1 'Mixed Catalyst-Substrate' Experiments

10.3.2 Insights from the Soai Reaction of a Fluoro-substituted Pyridine System

10.3.3 Inhibition of Autocatalysis by Excess Diisopropylzinc in the Pyridine Systems

10.4 Outlook: Competing Mechanistic Models

10.4.1 The Significance of Structure-Activity Relationships

10.4.2 The 'Hemiacetal Model'

10.4.3 Comparison and Critiques of the Hemiacetal Model and the Floor-to-Floor Model

10.5 Summary

Chapter 11 Elucidation of Soai's Asymmetric Autocatalysis

11.1 Introduction

11.2 Looking Back to the Beginning of Our Mechanistic Investigations on Soai's Asymmetric Autocatalysis: An Analysis

11.3 Kinetic Analysis

11.4 Identification and Reaction Progress Analysis of Intermediates of Soai's Asymmetric Autocatalysis by In Situ Reaction High-resolution Orbitrap Mass Spectrometry

11.5 The Doping Experiment: Formation of a Transient Catalyst During the Autocatalysis

11.6 Proposed Mechanism of Soai's Asymmetric Autocatalysis via the Formation of a Transient Hemiacetalate-catalyst

11.7 Evaluation of the Kinetic Data

11.8 Summary and Outlook

Chapter 12 Structure Analysis of Asymmetric Autocatalysis by X-ray Crystallography and Circular Dichroism Spectroscopy

12.1 Mechanism of Asymmetric Autocatalysis

12.2 Single Crystal X-ray Analysis of Zinc Alkoxide

12.2.1 Crystal Structures of Enantiopure and Racemic Tetramers

12.2.2 Structure of Oligomers.

12.2.3 Crystal Structure with Coordinative Solvent.

Notes:

Description based on publisher supplied metadata and other sources.

Description based on print version record.

Includes bibliographical references.

Other Format:

Print version: Soai, Kenso Asymmetric Autocatalysis

ISBN:

9781839166273

1839166274

9781839166280

1839166282