Yang - Deuterium: Discovery and Applications in Organic Chemistry

1. Tables in Chapter 1
2. Tables in Chapter 2
3. Tables in Chapter 3
4. Tables in Chapter 4
5. Tables in Chapter 5

1. Figures in Introduction
2. Figures in Chapter 2
3. Figures in Chapter 3
4. Figures in Chapter 4
5. Figures in Chapter 5
6. Figures in Conclusion

Jaemoon Yang

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To Urey and those who follow.

Jaemoon Yang, Ph.D., Cambridge Isotope Laboratories, Inc. Andover, MA

In the preparation of this book, I have received a great deal of assistance from many people. Without them this book would not have been possible.

I am pleased to acknowledge help from Professor Michael Krische of The University of Texas at Austin and Professor Takahiko Akiyama of Gakushuin University in Japan, who provided me with additional information on their research.

I would like to express my sincere appreciation to the following individuals at Cambridge Isotope Laboratories, Inc. (CIL): Dr. Joel Bradley instilled a great value of deuterium in me. Dr. William Wood encouraged me to explore a wonderful world of deuterium. Dr. Richard Titmas read the entire manuscript and made valuable suggestions. Mrs. Diane Gallerani obtained a number of rare articles in a timely manner. My colleagues at CIL, Drs. Sun-Shine Yuan, Susan Henke, Steven Torkelson, and Salim Barkallah, are gratefully acknowledged for their proofreading efforts and helpful comments.

I wish to thank the Elsevier publishing team for making the manuscript become a book. Katey Birtcher, senior acquisitions editor of chemistry, kindly accepted the book proposal and arranged a very smooth review process. Jill Cetel, senior editorial project manager, was instrumental ensuring that the book was ready to print.

Finally, I want to thank my wife, Wenjing Xu, PhD, for her support and love.

April 2016

It is everywhere around us. The water we drink every day is made up of hydrogen and oxygen, the gasoline we pump at the gas station contains hydrogen and carbon, the sugar we use is made of hydrogen, carbon, and oxygen. DNA is another fine example: it has hydrogen as well as other atoms such as carbon, nitrogen, oxygen, and phosphorus. Recently, hydrogen-fueled vehicles are gaining attention as a zero-emission alternative. Being the lightest of all the elements in the Periodic Table, hydrogen is one of the most common atoms that make up the world.

Since its discovery in 1766 by Henry Cavendish, hydrogen had been considered a pure element for more than 160 years. It turned out that hydrogen is not pure! It is very close to being pure, but it is not exactly 100%. The chemical purity of hydrogen is 99.985%. This is because there are two forms or isotopes of hydrogen: the protium accounts for 99.985% of naturally occurring hydrogen and the deuterium makes up the remaining 0.015%. When hydrogen is mentioned, it is usually referred to as protium, the major isotope of hydrogen.

As an isotope of hydrogen, deuterium exhibits the very same chemical properties as protium. On the other hand, deuterium has certain physical properties that are different from those of protium: it is twice as heavy as protium, which makes its bond to carbon or oxygen stronger than those attached to protium. Due to these unique properties, deuterium has been widely used in chemistry, biology, and physics.

The field of organic chemistry has benefited the most from the discovery of deuterium. One familiar example is the use of deuterated solvents such as deuteriochloroform (CDCl3) in nuclear magnetic resonance (NMR) spectroscopy. The proton NMR (1H NMR) spectrum of a sample provides valuable information about the structure of a molecule. In obtaining a proton NMR spectrum, a sample is typically dissolved in deuterated solvents such as deuteriochloroform. Obviously, deuterated solvent is required to clearly observe the signals arising from the analyte by obscuring the signal from the solvent.

Another application is the use of deuterium as a tracer in the study of reaction mechanism. With the use of deuterium-labeled compounds, organic chemists can conveniently follow the molecules to precisely figure out the reaction mechanism. An outstanding example can be found in a research paper published in 2010 by Professor Grubbs and coworkers at the California Institute of Technology. In studying the mechanism of ring-closing metathesis, the authors prepared a deuterium-labeled substrate (