This review summarizes advances in the decarboxylative alkylation of carboxylic acids and their derivatives under transition metal-free conditions in recent years. Unlike most transition metal-catalyzed decarboxylative coupling reactions which tend to undergo catalytic cycles, the mechanisms of reactions under metal-free conditions are usually diverse and even ambiguous in some cases. This article offers an overview of reaction types and their corresponding mechanisms, highlights some of the advantages and limitations, and focuses on introducing UV and visible light-induced, organocatalyst and peroxide promoted radical processes for decarboxylative alkylation and the formation of C–C bonds.

Transition metal-free decarboxylative alkylation reactions.

Chiral-at-Metal Rh(III) Complex-Catalyzed Decarboxylative Michael Addition of β-Keto Acids with α,β-Unsaturated 2-Acyl Imidazoles or Pyridine

Rhodium-catalyzed chemo- and regioselective decarboxylative addition of β-ketoacids to alkynes

Herein we disclose a silver-catalyzed [3 + 3] 1,3-dipolar cycloaddition reaction of trifluorodiazoethane with glycine imines. This reaction exhibits manifold remarkable features, such as easily ava...

Silver-Catalyzed [3 + 3] Dipolar Cycloaddition of Trifluorodiazoethane and Glycine Imines: Access to Highly Functionalized Trifluoromethyl-Substituted Triazines and Pyridines

The chemistry of cyclic imines has been gaining importance in the last decade because of their broad spectrum of applications and biological importance. This review focuses on the synthesis and utilization of these compounds with an emphasis on strategic transformations in organic chemistry. Electron-deficient sulfamate-derived and N-sulfonyl cyclic imines are also discussed as examples of versatile synthons in organic synthesis.

Cyclic imines – preparation and application in synthesis

Stereoselective Synthesis of Fused Aziridines via One-Pot Sequential Decarboxylative Mannich Reaction and Oxidative C-H Amination of Cyclic Imines with β-Ketoacids.

Introduction of oxygen vacancy to manganese ferrite by Co substitution for enhanced peracetic acid activation and 1O2 dominated tetracycline hydrochloride degradation under microwave irradiation

4-Anilinoquinazoline analogues stand out among many kinds of small molecules that inhibit the tyrosine kinase activities of epidermal growth factor receptor (EGFR), thus serving as significant molecular targets for anticancer drug design. Herein, a series of novel perfluorocarbon (PFC) modulated 4-anilinoquinazolines were designed and prepared straightforwardly by nucleophilic substitution reaction of various anilinoquinazolines and PFC-derived methanesulfonate. In the presence of base, the reaction proceeded smoothly to afford a wide range of 4-anilinoquinazolines with different substituents on aniline moiety in good to high yields. Furthermore, the PFC-modified analogues of gefitinib and erlotinib were also obtained in 93% and 90% respectively, which may have potential for developing new inhibitors of the epidermal growth factor receptor (EGFR) tyrosine kinase and fluorinated contrast agents (CA) for 19F MRI.

Facile Synthesis of Novel Perfluorocarbon‐Modulated 4‐Anilinoquinazoline Analogues

A novel one-pot sequential transformation via decarboxylative Mannich reaction (DMR) and oxidative C–H amination of cyclic imines with β-ketoacids is described. This methodology has been utilized to provide access to fused aziridines with excellent diastereoselectivity. Several examples of catalytic enantioselective sequential transformation are presented.

Stereoselective Synthesis of Fused Aziridines via One‐Pot Sequential Decarboxylative Mannich Reaction and Oxidative C—H Amination of Cyclic Imines with β‐Ketoacids.

Bo-Nan Lai

Papers

Stereoselective Synthesis of Fused Aziridines via One-Pot Sequential Decarboxylative Mannich Reaction and Oxidative C-H Amination of Cyclic Imines with β-Ketoacids.

Introduction of oxygen vacancy to manganese ferrite by Co substitution for enhanced peracetic acid activation and 1O2 dominated tetracycline hydrochloride degradation under microwave irradiation

Facile Synthesis of Novel Perfluorocarbon‐Modulated 4‐Anilinoquinazoline Analogues

Stereoselective Synthesis of Fused Aziridines via One‐Pot Sequential Decarboxylative Mannich Reaction and Oxidative C—H Amination of Cyclic Imines with β‐Ketoacids.