Green Oxidation in Organic Synthesis

Ning Jiao, Shannon S. Stahl, Ning Jiao, Shannon S. Stahl

• Publisher: Wiley
• Year: 2019
• Print ISBN: 9781119304166
• eBook ISBN: 9781119304043
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Chemistry
• Index: Chemistry

A valuable introduction to green oxidation for organic chemists interested in discovering new strategies and new reactions for oxidative synthesis

Green Oxidation in Organic Synthesis provides a comprehensive introduction and overview of chemical preparation by green oxidative processes, an entry point to the growing journal literature on green oxidation in organic synthesis. It discusses both experimental and theoretical approaches for the study of new catalysts and methods for catalytic oxidation and selective oxidation.

The book highlights the discovery of new reactions and catalysts in recent years, discussing mechanistic insights into the green oxidative processes, as well as applications in organic synthesis with significant potential to have a major impact in academia and industry. Chapters are organized according to the functional groups generated in the reactions, presenting interesting achievements for functional group formation by green oxidative processes with O 2, H 2 O 2, photocatalytic oxidation, electrochemical oxidation, and enzymatic oxidation. The mechanisms of these novel transformations clearly illustrated.

Green Oxidation in Organic Synthesis will serve as an excellent reference for organic chemists interested in discovering new strategies for oxidative synthesis which address the priorities of green and sustainable chemistry.

1
Green Oxidative: Synthesis of Alcohols and Phenols

Tianlei Li, Tianlong Lan, Liguo Wang, and Yu Rao

Tsinghua University, Beijing, China

1.1 Introduction

Alcohol and phenol derivatives are among the most important and common organic chemicals used for industrial materials such as polymers and commodity chemicals, and are the core structures of many biologically active compounds, including pharmaceuticals, agrochemicals, and natural products. The development of synthetic methods for introducing hydroxyl groups into organic compounds is a fundamental task in organic chemistry. Due to the sustainable chemistry and environmentally friendly manufacturing techniques extensively demanded in society today, development of new synthetic methodologies and novel reaction conditions without compromising product selectivity, energy efficiency, and environmental safety has become the main theme of current chemical research. Over the past decades, numerous methods have been reported, the most important and straightforward strategy is the oxidation of various C─H, C─C, and C═C bonds to hydroxyl groups. In this review, we will focus on the latest developments adopting green oxidative strategies with aerobic (O₂ and air), hydrogen peroxide, enzymatic oxidation, and photocatalytic oxidation for synthesis of alcohol and phenol derivatives that have happened since 2008. Mechanistic studies of the novel transformations including the preparation and isolation of reaction intermediates will also be discussed. Our intention is to highlight here the interesting achievements in green oxidative synthesis of alcohols and phenols over the last 10 years. There may be important literature reports that have escaped our attention, for which we extend our sincere apologies.

1.2 C─H Hydroxylation via Aerobic Oxidant

C─H hydroxylation is considered as one of the most straightforward approaches to preparing alcohols and phenols. During this process, various oxidants, such as inorganic salt, TBHP, PhI(OAc)₂, K₂S₄O₈, and IBX, are used. For green and sustainable chemistry, molecular oxygen is considered as an ideal oxidant due to its natural, inexpensive, and environmentally friendly characters, and therefore offers attractive academic and industrial prospects. In addition, it exhibits a highly atom‐efficient oxidant per weight. In this context, various significant progress in catalytic C─H hydroxylation via aerobic oxidant has been achieved over the past 10 years, especially in transition metal‐ (such as palladium, copper, and cobalt) catalyzed oxidation reactions employing molecular oxygen as the sole oxidant. In the next section, we will illustrate the recent advances over the last 10 years in C─H hydroxylation using molecular oxygen or air as an oxidant.

1.2.1 Synthesis of Phenols by C(sp²)‐H Hydroxylation

An intriguing example of employing transition metals to catalyze ortho‐hydroxylation involving strong coordination of the carbonyl group was reported by Yu and co‐workers in 2009 [1]. Notably, hydroxylation proceeded using 1 atm of air as the sole oxidant under nonacidic conditions in high yields with variously substituted benzoic acids such as trifluoromethyl, acetyl, cyanide, and nitro. Preliminary mechanistic investigations strongly supported the proposal that the aryl‐Pd species could be directly oxygenated by molecular O₂ (Scheme 1.1).

Scheme 1.1 Pd(II)‐catalyzed hydroxylation of arenes with 1 atm of O₂ or air.

In 2012, Lei’s group reported a copper‐catalyzed “oxygenase‐type” oxidation of arenes and heteroarenes at room temperature by the oxidation of O₂ from air (1 atm). The authors proposed a mecha...

Table of contents

• Cover
• Table of Contents
• Preface
• List of Contributors
• 1 Green Oxidative
• 2 Green Oxidative Synthesis of Aldehydes and Ketones
• 3 Green Oxidative Synthesis of Ethers, Esters, and Organic Halides
• 4 Green Oxidative Synthesis of Epoxides
• 5 Green Oxidative Synthesis of Carboxylic Acids
• 6 Green Oxidative Synthesis of Amines, Amides, and Imines
• 7 Green Oxidative Synthesis of Nitriles
• 8 Green Oxidative Synthesis of Azo, Diazo, and Azido Compounds
• 9 Green Oxidative Synthesis of Substituted Olefins and Alkynes
• 10 Green Oxidative Synthesis of Substituted Arenes
• 11 Green Oxidative Synthesis of Heterocyclic Compounds
• 12 Green Oxidation of Sulfide to Sulfoxide and Sulfone
• 13 Oxidative Couplings with C─H Bonds Forming C─P and C─S Bonds
• 14 The Recent Developments of Photocatalytic Oxidation
• 15 The Recent Developments of Electrochemical Oxidation
• 16 The Recent Developments of Enzymatic Oxidation
• Index
• End User License Agreement