Amination and Formation of sp2 C-N Bonds

Table of Contents

1. Frontmatter

2. Palladium-Catalyzed sp2 C–N Bond Forming Reactions: Recent Developments and Applications

   Georgia S. Lemen, John P. Wolfe

   Abstract

   This review describes recent developments in the field of Pd-catalyzed sp² C–N bond formation that were reported in the primary literature between 2004 and 2008. These transformations have found widespread application in both academia and industry. A brief history of the field is presented, followed by recent improvements and extensions of the methodology. Applications of these transformations to the synthesis of useful compounds, including biologically active molecules, and materials, are described.

3. Metal-Catalyzed C(sp2)–N Bond Formation

   Arkaitz Correa, Carsten Bolm

   Abstract

   During the last decades a powerful set of protocols featuring C(sp²)–N bond formation have emerged as convenient alternatives for the assembly of enamine and enamides. Those methods consist of mostly palladium-catalyzed oxidative amidations of alkenes and both palladium- and copper-catalyzed cross-couplings between generally vinyl halides or pseudohalides and amines or amides. In this review recent advances in both types of processes will be disclosed. Additionally, the synthetic value of the title processes will be illustrated by describing relevant total syntheses of natural products involving vinylation process as the key step.

4. Assembly of N-Containing Heterocycles via Pd- and Cu-Catalyzed C–N Bond Formation Reactions

   Yongwen Jiang, Dawei Ma

   Abstract

   Some newly developed methods for assembling N-containing heterocycles are summarized here. The key transformations in these methods are Pd- or Cu-catalyzed N-arylation and N-vinylation. The heterocycles include indoles, benzimidazoles, pyrroles, indazoles, indolines, lactams, quinazolinones and heterobenzazepines. These conceptually-novel and reliable methods should find applications in the synthesis of bioactive compounds and material molecules.

5. Recent Developments in Recyclable Copper Catalyst Systems for C–N Bond Forming Cross-Coupling Reactions Using Aryl Halides and Arylboronic Acids

   Mannepalli Lakshmi Kantam, Chintareddy Venkat Reddy, Pottabathula Srinivas, Suresh Bhargava

   Abstract

   This review covers the recent recyclable protocols for the C–N bond forming reactions between aromatic, heterocyclic and aliphatic amines such as imidazoles, benzimidazoles, benzylamines, piperidine, pyrrole, imides, anilines, hexyl, cyclohexyl amines, and amides as coupling partners with aryl iodides, bromides, chlorides, and arylboronic acids employing copper-mediated systems. The physical properties and characterization of the catalysts and their use in organic synthesis will be outlined. Most importantly, these recyclable versions developed by many groups in the recent years are potential candidates for commercial exploitation. The effect of additives, solvents, temperature, base, the nature of aryl halides on reactivity, and recycle studies of the heterogeneous catalysts are included in this review. We believe that this information is beneficial for the people who are doing similar studies in this field. Catalyst optimization is of critical importance to catalyst development, thus the information we have included in this review contains very valuable information for the newcomers to the field. To our knowledge this is the first review that covers the title chemistry.

6. Copper-Catalyzed C(aryl)–N Bond Formation

   Florian Monnier, Marc Taillefer

   Abstract

   Although requiring the use of stoichiometric amounts of metal and harsh conditions, the copper-mediated coupling reactions of aryl halides with amines and phenols (Ullmann condensations), amides and carbamates (Ullmann–Goldberg condensations), or activated methylene compounds (Ullmann–Hurtley condensations) have been for a long time useful methods for the formation of C(aryl)–N, C(aryl)–O, and C(aryl)–C bonds. In 2001, a renaissance of the Ullmann reaction has been initiated with the discovery of versatile new copper catalytic systems for C–C, C–N, or C–O coupling under mild temperature conditions.

   This chapter covers more specifically the copper-catalyzed C(aryl)–N bond formation via the coupling of aryl halides with nitrogen nucleophiles such as N-heterocycles, amines, anilines, amides, ammonia, azides, hydroxylamines, nitrite salts or phosphonic amides. The C(aryl)–N bond formation as a result of the coupling between these nucleophiles and arylboronic acids (the Chan–Lam reaction) will be also presented. It is worth noting that this chapter mainly focuses on the most significant results and important breakthroughs in this field.

7. Backmatter