Oxygen: The Key to Stereoelectronic Control in Chemistry
Author(s):
- Igor AlabuginDistinguished Research ProfessorFlorida State UniversityEmail: [email protected]More by Igor Alabugin
Publication Date:
May 24, 2023
Copyright ©
2023 American Chemical Society
eISBN:
9780841299634
DOI:
10.1021/acsinfocus.7e7009
Read Time:
six to seven hours
Collection:
2
Publisher:
American Chemical Society
Although carbon is considered the central element of organic chemistry, the broader chemical world has one more star player—oxygen. Billions of years of evolution have filled your room with oxygen as countless cyanobacteria and plants work on changing our planet. Oxygen is everywhere—from geology to biology, from the Earth's crust to the ozone layer.
This digital primer aims to analyze chemical reactivity through the prism of oxygen chemistry. The key to understanding this chemistry is the lone pairs of oxygen (i.e., the underutilized "idle" electrons that do not directly contribute to the Lewis structure of molecules). By highlighting the many roles of oxygen, we will illustrate how chemistry rises above the limitations of Lewis structures and how electrons stay neither idle nor "lone" even if they are in "lone pairs" when an oxygen atom is near a reaction center. This digital primer will introduce important types of chemical bonding that transcend undergraduate textbooks but that are likely to drive the development of new chemical reactions in the future.
This book is coming soon. In the meantime, please contact your library or ACS sales representative for purchase options.
Detailed Table of Contents
About the Series
Preface
Chapter 1
Oxygen: An Element of Many Surprises
1.1
Introduction
1.2
The Importance of Oxygen
1.3
Oxygen Chemistry Is Full of Surprises
1.4
Chemical Bonds of Carbon and Oxygen
1.4.1
Mixing Carbon and Oxygen Is Good, Especially When Making a C=O (Carbonyl) Group
1.4.2
A Deeper Look at C–C, C–O, and O–O Single Bonds
1.5
The Diversity of Reactive Oxygen Species
1.6
Oxygen as a Chemical Chameleon: The Diversity of Functional Groups and Reactivity Patterns
1.7
Conclusion
1.8
That’s a Wrap
1.9
Test Your Understanding
1.10
Read These Next
Chapter 2
What Are Stereoelectronic Effects, and How Can We Control Them?
2.1
Introduction
2.2
What Are Stereoelectronic Effects?
2.3
A Short Intro to “Classical” Chemical Bonding: The Shared Electron Pair Paradigm and Beyond…
2.4
Types of Stereoelectronic Interactions
2.4.1
Conjugation, Hyperconjugation, and σ-Conjugation
2.4.2
Positive, Negative, and Neutral Hyperconjugation
2.4.3
Geminal, Vicinal, and Remote Interactions
2.5
Factors Controlling SEs
2.5.1
Orbital Symmetry and Spatial Overlap
2.5.2
Acceptor/Donor Ability
2.5.3
Acceptor Ability: The Effects of Electronegativity and Bond Strength
2.5.4
Anisotropy of Acceptor Orbitals
2.5.5
Donor Properties
2.6
Conclusion
2.7
That’s a Wrap
2.8
Test Your Understanding
2.9
Read These Next
Chapter 3
Structural, Spectroscopic, and Chemical Manifestations of Stereoelectronic Effects
3.1
Introduction
3.2
Structural Manifestations
3.2.1
Bond Lengths
3.2.2
Physical Properties
3.3
Spectroscopic Manifestations
3.3.1
Infrared (IR) Spectroscopy—Bohlmann Effects
3.3.2
Nuclear Magnetic Resonance (NMR) Spectroscopy: Perlin and Isotope Effects
3.3.2.1
Perlin Effect
3.3.2.2
Isotope Effects
3.4
Reactivity
3.5
Reaction Kinetics
3.6
That’s a Wrap
3.7
Test Your Understanding
3.8
Read These Next
3.9
Insider Q&A: Eusebio Juaristi
Chapter 4
Models and Theoretical Studies of Stereoelectronic Effects
4.1
Introduction
4.2
Conformational Changes
4.3
Bond Breaking/Bond Forming Equations: BDEs, pKas, and Hydride Affinities
4.4
Thermochemical Equations
4.4.1
Isogyric Equations
4.4.2
Isodesmic Equations
4.4.3
Homodesmotic Equations
4.5
Exploring Electronic Interactions through Wavefunction Analysis
4.5.1
Natural Bond Orbitals
4.5.2
Energy Decomposition Analysis
4.5.3
Natural Energy Decomposition Analysis
4.5.4
Block-Localized Wavefunctions
4.6
That’s a Wrap
4.7
Test Your Understanding
4.8
Read These Next
4.9
Insider Q&A: Frank Weinhold
Chapter 5
Organic Chemistry Through the Prism of SEs: Functional Groups with One Oxygen
5.1
Introduction
5.2
Alcohols
5.2.1
Impact of Alcohol Group on the α-C–H BDE
5.2.2
Carbenium Ion Formation
5.2.3
Tuning the Donor Ability of Alcohol
5.2.4
Anionic Oxygen—Donor without Stereoelectronic Restrictions
5.3
Ethers
5.3.1
BDE and H-Atom Abstraction
5.3.2
Other Reactions with Neutral Reactive Intermediates
5.3.3
Hydride Transfer
5.3.4
Oxygen as an Acceptor
5.4
Aldehydes and Ketones
5.4.1
C–H Activation
5.4.2
Tuning H-Abstraction
5.5
That’s a Wrap
5.6
Test Your Understanding
5.7
Read These Next
Chapter 6
Organic Chemistry Through the Prism of SEs: Functional Groups with Two Oxygens
6.1
Introduction
6.2
Acetals and Hemiacetals
6.2.1
Conformational Preferences
6.2.2
Reactions of Acetals
6.2.3
Radical Reactions
6.2.4
Hemiacetals, Gem-Diols, and Tetrahedral Intermediates
6.3
Carboxylic Acids
6.3.1
Conformational Preference
6.3.2
The Role of H-Bonding in Conformational Preferences
6.3.3
Syn/Anti Lone Pairs & Basicity
6.4
Esters
6.4.1
Lactones
6.4.2
Acceptor Ability of C–O Bonds
6.5
Peroxides: The Stereoelectronic Key to Stabilization
6.6
That’s a Wrap
6.7
Test Your Understanding
6.8
Read These Next
Chapter 7
O2, O3, CO2: Simple but Surprising Molecules that Take Us Beyond 2-Center, 2-Electron Bonds
7.1
Introduction
7.2
2-Center, 3-Electron Bonds: A New Type of Bond
7.3
Why Can’t We Build Large Molecules Entirely from Oxygen?
7.4
Three-Electron Bonds as the Key to Selective Reactions
7.4.1
Amplifying 3e-Stabilization by Deprotonation, H-Bonding, and Activation of C–C Bonds
7.4.2
3e-Bonds as a Key to Electron Upconversion
7.4.3
Supramolecular Effects with 3e-Bonds – Design of Directing Groups for Radical Additions and Fragmentations
7.5
O3 and CO2: The Emergence of 3c,4e-Bonding
7.6
That’s a Wrap
7.7
Test Your Understanding
7.8
Read These Next
Bibliography
Glossary
Index
Reviewer quotes
As an organic chemist, I've always held carbon in the highest regards, but this primer made me a lot more interested in furthering my understanding of the stereoelectronic effects of oxygen. Since oxygen is used quite a bit as a means of controlling reactivity, furthering this understanding will drive me to come back to this primer. There is a lot of great information in the primer.
I would recommend this work to all undergrads with bioorganic chemistry major, PhD students and post-doctoral fellows doing their research in chemical biology, bio-organic chemistry, biochemistry and organic chemistry, university professors and teachers.
Igor Alabugin grew up in Siberia and earned his Ph.D. degree from Lomonosov Moscow State University. After a postdoctoral study at the University of Wisconsin-Madison, he joined the FSU Department of Chemistry and Biochemistry in 2000 where he is currently the Distinguished Research Professor. Professor Alabugin research uncovers new connections between chemical structure and reactivity, often associated with stereoelectronic effects. His interests span development of cascade transformations, design of light- and pH-activated molecules, construction of carbon-rich nanostructures, and establishing the roles of electron upconversion in catalysis. In addition to >200 publications, he gave >200 talks at conferences, universities, and industries. He is the recipient of three FSU Undergraduate Awards: Teaching, Advising, and Research Mentor. His research accomplishments were recognized by American Chemical Society (ACS) Cope Scholar Award, Markovnikov Medal, George Gamow Medal, ACS Florida Award, AAAS and Fulbright Fellowships.
Leah R. Kuhn is a graduate student working under the supervision of Prof. Alabugin at Florida State University. She received her B.Sc. in Chemistry in 2019 from Miami University and her M.Sc. from Florida State University in 2022. She received the NSF GRFP award in 2021 which has funded her graduate research. Her research involves the use of computational methods to explore organic reactions, specifically focusing on the stereoelectronic effects of oxygen.
