Carbonylation basic principles

Abstract The basic principles of the oxidative carbonylation reaction together with its synthetic applications are reviewed. In the first section, an overview of oxidative carbonylation is presented, and the general mechanisms followed by different substrates (alkenes, dienes, allenes, alkynes, ketones, ketenes, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, phenols, amines) leading to a variety of carbonyl compounds are discussed. The second section is focused on processes catalyzed by Pdl2-based systems, and on their ability to promote different kind of oxidative carbonylations under mild conditions to afford important carbonyl derivatives with high selectivity and efficiency. In particular, the recent developments towards the one-step synthesis of new heterocyclic derivatives are described. 

The special case of hydrogen abstraction has been discussed in connection with the simple model for the n-n excited state. However, it was noted in 1959-62 by Zimmerman 1 -3,7) that a major fraction of the organic photochemistry of carbonyl compounds was explicable on the basis of simple basic principles and this simple model for the carbonyl group. 

The number and complexity of structural types that can arise via polyketides is magnified when one realizes that other reactions involving the carbon chain and its carbonyl groups can precede or follow cyclization. Although the number of polyketides for which precise biosynthetic details are known is limited, reasonable suggestions can be made as to their main elements based on a few basic principles of organic reaction mechanisms. 

Basic Principles Practical Photochemistry General Considerations Carbonyl Compounds a-Cleavage Carbonyl Compounds Hydrogen Abstraction ... 

Nucleophilic addition to the C-O double bond of carbonyl derivatives is one of the most widely used C-C-bond forming reactions in organic synthesis. The synthetic value of this process lies particularly on the stereocontrolled formation of a new C-O-chiral center when aldehydes or ketones are used. On the other hand, carbonyl derivatives themselves can serve as nucleophiles leading to new carbon-carbon bonds and thus expanding the synthetic scope of these functional groups. The explanation of the underlying basic principles in terms of reactivity and stereochemical models is beyond the scope of this book and will not be discussed in the following chapter since many textbooks cover these issues. Instead, we wish to provide the practitioner with examples that detail the delicate relationship of an individual, unique structure with its special reactivity delineated thereof... 

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