The main contributions in the field of first-row transition-metal-catalyzed (base-metal-catalyzed) carbonylative transformations have been summarized and discussed. The contents have been divided according to the electrophiles applied, followed by the different types of nucleophiles. Their reaction mechanisms and applications have been emphatically discussed.

First-Row Transition-Metal-Catalyzed Carbonylative Transformations of Carbon Electrophiles.

α,β-Unsaturated carbonyl compounds are key building blocks in organic chemistry. Their catalytic synthesis has received significant attention during the past decades. Among the known methodologies, carbonylation reactions represent an atom-efficient tool box to convert a variety of easily available substrates into valuable α,β-unsaturated carbonylated products including aldehydes, ketones, esters, amides, and carboxylic acids. Herein, we summarize the most important achievements in this field with a special focus on results from the last decade.

Synthesis of α,β-unsaturated carbonyl compounds by carbonylation reactions

Natural product syntheses via carbonylative cyclizations

Enantioenriched indole derivatives are widely found in natural products, pharmaceuticals and bioactive compounds. Therefore, developing efficient methods for the synthesis of enantioenriched indole derivatives has become an important goal in the community of organic chemistry. To this end, chemists have designed and developed a variety of indole-containing platform molecules and their related catalytic asymmetric reactions. Among these approaches, vinylindoles have proved to be versatile platform molecules for accessing enantioenriched indole derivatives via catalytic asymmetric reactions, especially organocatalytic asymmetric reactions. Based on this approach, a plethora of chiral indole derivatives have been synthesized with optical purity and structural complexity. This review summarizes advances in vinylindole-based organocatalytic asymmetric reactions since 2008 and includes the applications of some methodologies in the total synthesis of natural products. In addition, this review points out the remaining challenges in this research area to be confronted by organic chemists, which will shed light on the future development of this area.

Advances in organocatalytic asymmetric reactions of vinylindoles: powerful access to enantioenriched indole derivatives

Water excellent solvent for the synthesis of bifunctionalized cyclopentenones from furfural

The cyclopentenone unit is a very powerful synthon for the synthesis of a variety of bioactive target molecules. This is due to the broad diversity of chemical modifications available for the enone structural motif. In particular, chiral cyclopentenones are important precursors in the asymmetric synthesis of target chiral molecules. This Review provides an overview of reported methods for enantioselective and asymmetric syntheses of cyclopentenones, including chemical and enzymatic resolution, asymmetric synthesis via Pauson-Khand reaction, Nazarov cyclization and organocatalyzed reactions, asymmetric functionalization of the existing cyclopentenone unit, and functionalization of chiral building blocks.

Krassimira P. Guerra

Papers

Synthesis of Chiral Cyclopentenones.

An efficient and simple Morita–Baylis–Hillman reaction based on the N-methylpyrrolidine–Ba(OH)2 catalytic system

Synthesis of Chiral Cyclopentenones

Efficient Tandem Morita–Baylis–Hillman/Double Cross-Aldol Reaction between Cyclic Enones and Formaldehyde Promoted by N-Methylpyrrolidine

Synthetic Survey and Activity of 2′‐Deoxy‐methanocarba Nucleosides