Nickel Catalysis in Organic Synthesis

Methods and Reactions

Sensuke Ogoshi

• Publisher: Wiley-VCH
• Year: 2019
• Print ISBN:
  9783527344079
• eBook ISBN:
  9783527813810
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Physical & Theoretical Chemistry

A comprehensive reference to nickel chemistry for every scientist working with organometallic catalysts

Written by one of the world?s leading reseachers in the field, Nickel Catalysis in Organic Synthesis presents a comprehensive review of the high potential of modern nickel catalysis and its application in synthesis. Structured in a clear and assessible manner, the book offers a collection of various reaction types, such as cross-coupling reactions, reactions for the activation of unreactive bonds, carbon dioxide fixation, and many more.

Nickel has been recognized as one of the most interesting transition metals for homogeneous catalysis. This book offers an overview to the recently developed new ligands, new reaction conditions, and new apparatus to control the reactivity of nickel catalysts, allowing scientists to apply nickel catalysts to a variety of bond-forming reactions. A must-read for anyone working with organometallic compounds and their application in organic synthesis, this important guide:

-Reviews the numerous applications of nickel catalysis in synthesis
-Explores the use of nickel as a relatively cheap and earth-abundant metal
-Examines the versatility of nickel catalysis in reactions like cross-coupling reactions and CH activations
-Offers a resource for academics and industry professionals

Written for catalytic chemists, organic chemists, inorganic chemists, structural chemists, and chemists in industry, Nickel Catalysis in Organic Synthesis provides a much-needed overview of the most recent developments in modern nickel catalysis and its application in synthesis.

Part I
Reactions via Nickelacycles

1
Formation of Nickelacycles and Reaction with Carbon Monoxide

Sensuke Ogoshi

Osaka University, Department of Applied Chemistry, Suita, Osaka, 565-0871, Japan

1.1 Introduction

Oxidative cyclization is one of the most efficient methods to form carbon–carbon bonds in one step. For example, the trimerization of alkynes to afford arenes catalyzed by a variety of transition metals has been well known as a part of Reppe chemistry, in which the oxidative cyclization of two alkynes with a transition metal to generate a metalacyclopentadiene has been believed to be a key step and might be the most common oxidative cyclization reaction. The reaction of metalacyclopentadiene with carbon monoxide is one of the logical extensions of trimerization of alkynes. The first Pauson–Kahnd-type reaction was reported in 1960 – the reaction of Fe(CO)₅ with acetylene to afford the corresponding (η⁴-cyclopentadienone)iron complex (Figure 1.1) [1]. In general, the reaction of metal carbonyls with alkynes gives η⁴-cyclopentadienone metal complexes. However, the coordination of η⁴-cyclopentadienone is too strong to dissociate spontaneously, which makes the expansion of a stoichiometric reaction to a catalytic reaction difficult. On the other hand, both stoichiometric and catalytic Pauson–Kahnd reactions have been reported in 1973 at the same time (Figure 1.2) [2]. This reaction has been developed as a step economy method for the construction of cyclopentenones in one step, including optically active complicated compounds [3]. The minimum requirement for transition metals to promote the Pauson–Kahnd-type reactions is the formation of metalacycles and the following insertion of carbon monoxide and reductive elimination to give the corresponding carbonyl compounds. Thus, the synthesis of a variety of cyclic carbonyl compounds such as lactams and lactone by the catalytic hetero-Pauson–Kahnd reactions seems a logical extension.

1.2 Formation of Hetero-nickelacycles from Nickel(0)

As mentioned above, the first catalytic Pauson–Kahnd reaction had been reported at the same time as the first stoichiometric Pauson–Kahnd reaction. In contrast, to date, a very limited number of examples of the catalytic hetero-Pauson–Kahnd reactions to afford lactones and lactams have been reported, due to the less transition metals that can form hetero-metalacycles by oxidative cyclization with carbonyl compounds or imines (Figure 1.3) [4–8]. In that sense, nickel is one of the most promising transition metals as a catalyst for the hetero-Pauson–Kahnd reaction. In fact, the formation of a variety of hetero-nickelacycles has been reported. In addition, oxidative addition of strained small ring compounds also affords nickelacycles (Figure 1.4) [9–11].

Figure 1.1 Formation of (η⁴-cyclopentadienone)iron complex.

Figure 1.2 Cobalt-catalyzed Pauson–Kahnd reaction.

Figure 1.3 Formation of nickelacycles by oxidative cyclization.

Figure 1.4 Formation of nickelacycles by oxidative addition.

1.3 Stoichiometric Reaction of Hetero-nickelacycles with Carbon Monoxide

In general, nickel tetra-carbonyl complex, Ni(CO)₄, might be the most famous metal carbonyl complex owing to the very high toxicity and its usage for the purification of nickel metal. In addition, Tolman's electronic parameter (TEP) has been evaluated by using a variety of nickel carbonyl complexes, Ni(CO)₃L or Ni(CO)₂L₂. These facts indicate that organonickel complexes can react with carbon monoxide to give Ni(CO)₃L or Ni(CO)₂L₂ easily. In fact, the reaction of hetero-nickelacycles with carbon monoxide affords a variety of expected cyclic carbonyl compounds quantit...

Table of contents

• Cover
• Table of Contents
• Preface
• Part I: Reactions via Nickelacycles
• Part II: Functionalization of Unreactive Bonds
• Part III: Coupling Reactions via Ni(I) and/or Ni(III)
• Part IV: Carbon Dioxide Fixation
• Index
• End User License Agreement