Jean-Baptiste Sortais (editor) - Manganese Catalysis in Organic Synthesis

1. Chapter 4
2. Chapter 5
3. Chapter 10

1. Chapter 1
2. Chapter 2
3. Chapter 3
4. Chapter 4
5. Chapter 5
6. Chapter 6
7. Chapter 7
8. Chapter 8
9. Chapter 9
10. Chapter 10

Edited by

Jean-Baptiste Sortais

Editor

Prof. Jean-Baptiste Sortais
University of Toulouse III
CNRS (LCC) - UPR 8241
205 route de Narbonne
31077 Toulouse, cedex 4
France

Cover

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Homogeneous catalysis using transition metal complexes has been in continuous development since the late 1960s. These great achievements have conferred to organometallic catalysis a central role in organic synthesis, as a powerful tool not only to promote new reactions but also to develop highly chemo-, regio-, and enantioselective transformations, resulting in the award of three Nobel Prizes in the field of homogeneous catalysis at the beginning of this century in less than 10years (2001, 2005, and 2010). Most of the historic advances were realized with noble metals, laying the groundwork for basic reactions of organometallic chemistry and mechanisms in catalysis. However, over the last 20years, the evolution of economic, geopolitical, and environmental constraints, as well as scientific curiosity, has paved the way for the use of non-noble transition metals in homogeneous catalysis. The chemistry of iron, the most abundant transition metal, was one of the first to be revisited in the light of sustainable development, and fantastic advances have been made in a short period of time. Nickel, cobalt, and copper have also experienced a resurgence of interest. On the opposite, while manganese compounds are generally known as stoichiometric oxidation reagents (KMnO4 or MnO2), their use in homogeneous catalysis has been less investigated compared with other late 3d transition metals, albeit manganese has several advantages. Manganese is indeed the third most abundant transition metal after iron and titanium, with an abundance of about 1000ppm in the Earth's crust. Unlike cobalt, this metal is not considered a critical resource by the European Union, i.e. there is no supply risk, nor too much price volatility, which is a recurrent issue with precious metals. It is also a heavy metal with low toxicity, as evidenced by the oral permitted daily exposure (PDE) of 250ppm according to the European Medicines Agency. This is an undeniable advantage when considering late state transformations in drug synthesis without extensive purification to remove metal residues. Finally, manganese has the widest range of oxidation states of the metals in the first row of block d, from III to +VII, a large playground for developing efficient catalysts when combined with the properly designed ligand. All these appealing characteristics make manganese an ideal candidate to build up complementary catalysts compared with the other 3d metals.

The aim of this book is to give the reader a general overview of what is possible to achieve in homogeneous catalysis with manganese-based catalysts nowadays. It will address various aspects: from organometallic precursors to applications in organic synthesis. The areas covered, in terms of transformations, are spanning from reduction to oxidation; from CC, CN, and CX bond formations; and from cross-coupling reactions to CH bond activations, including photo- and electrochemical transformations. My personal feeling is that the state of the art regarding manganese can be compared to some extent with the case of iron a decade ago, when the book titled Iron Catalysis in Organic Chemistry: Reactions and Applications edited by Dr. Bernd Plietker was published by Wiley in 2008. I hope that reading the present book will be highly stimulating for specialists and non-specialists in the field.

As editor, I would like to warmly thank all contributors to this book, for their participation and their enthusiasm in this project and, in some cases, for their patience, as a global pandemic attempted to slow the project down. I also acknowledge the support of the staff from Wiley VCH, namely, Anne Brenfuehrer, Elke Maase, and Katherine Wong.

Toulouse, France

15th December 2020

Alina A. Grineva

LCC-CNRS, Universit de Toulouse, CNRS, 31077 Toulouse cedex 4, France

Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky Pr., Moscow, 119991 Russia

Organometallic manganese chemistry emerged in 1937 with the in situ generation of the first Mn(II) species, PhMnI, and therefore it will not be covered in our contribution. Even if the chemistry of Mn(I) complexes directed to organic synthesis is much less developed, some interesting results have been obtained during the last 30years, but they have never been systematically reviewed. The main goal of this chapter is to provide an overview of the multiple facets of manganese organometallic chemistry, from the information on various metallic precursors and basic reactivity patterns to the design of Mn-containing chiral ligands and application of Mn(I)-mediated processes in organic synthesis.

Unlike more electropositive alkaline and alkaline earth metals, commercial manganese powder undergoes the insertion across Chalogen bond to form organometallic RMnX species uniquely for highly activated allylhalides and -halogenated esters under Barbier conditions was shown to generate in situ a very reactive form of metallic manganese, capable of activating a variety of alkenyl-, aryl-, and heteroarylhalide substrates under mild conditions.