The 3,3′-disubstituted oxindole structural motif is a prominent feature in many alkaloid natural products, which include all kinds of tetrasubstituted carbon stereocenters, spirocyclic or not, all-carbon or heteroatom-containing. The catalytic asymmetric synthesis of the tetrasubstituted carbon stereocenter at the C-3 position of the oxindole framework integrates new synthetic methods and chiral catalysts, reflects the latest achievements in asymmetric catalysis, and facilitates the synthesis of sufficient quantities of related compounds as potential medicinal agents and biological probes. This review summarizes the recent progress in this area, and applications in the total synthesis of related bioactive compounds.

Catalytic Asymmetric Synthesis of Oxindoles Bearing a Tetrasubstituted Stereocenter at the C‐3 Position

2. Essential Components: Earlier Developments 5449 2.1. Activated alkenes/alkynes 5450 2.1.1. Acyclic activated alkenes/ alkynes 5450 2.1.2. Cyclic activated alkenes 5451 2.2. Electrophiles 5451 2.3. Catalysts 5452 3. Essential Components: Recent Developments 5452 3.1. Activated Alkenes/Alkynes 5452 3.2. Electrophiles 5460 3.3. Catalysts 5477 4. Asymmetric Baylis-Hillman Reaction: Earlier Developments 5495

Recent contributions from the Baylis-Hillman reaction to organic chemistry.

Selective cleavages of carbon-carbon bonds catalyzed by transition-metal complexes have been shown to be increasingly versatile tools for organic synthesis allowing for complementary synthetic strategies Numerous examples of transition-metal catalyzed C-C bond activations of three- and four-membered ring systems have been reported These strained rings have been shown to engage in a variety of new ring-opening rearrangements and cycloaddition reactions leading to valuable structures Besides strain-driven transformations, other facilitating strategies to enforce the C-C bond activation of unstrained molecules have been developed as well While the variety of different transformations is less abundant, they concentrate on chelation-assisted reactions using appropriate permanent or transient directing groups In particular, the cleavage and subsequent functionalization of the C-CN bonds and decarbonylation processes operating by an excision of carbon monoxide from ketone derivatives have witnessed a large progress

Catalytic C-C Bond Activations via Oxidative Addition to Transition Metals.

Recent Advances in Transition-Metal-Catalyzed Functionalization of Unstrained Carbon–Carbon Bonds

Metal-catalysed cleavage of carbon–carbon bonds

Chemoselectivity in catalytic C-C and C-H bond activation: controlling intermolecular carboacylation and hydroarylation of alkenes.

https://pubs.acs.org/doi/pdf/10.1021/ol201259g

Highly enantioselective intramolecular cyanoamidation: (+)-horsfiline, (-)-coerulescine, and (-)-esermethole.

Notable features of the title process are the use of [Rh(cod)2]BF4/dppe catalyst system as well as the quinoline chelating group to suppress the competitive decarbonylation reaction.

Insertion of an alkene into an ester: intramolecular oxyacylation reaction of alkenes through acyl C-O bond activation.

A short protocol for the practical scale synthesis of several ω-borono-α-amino acids is described via the alkylation of benzophenone glycinimines with various electrophiles.

Concise synthesis of ω-borono-α-amino acids

RETRACTED: Catalytic C–CN activation and asymmetric cyanoamidation of alkenes: total syntheses of (+)-horsfiline, (−)-coerulescine, and (−)-esermethole

Venkata Jaganmohan Reddy

Papers

Chemoselectivity in catalytic C-C and C-H bond activation: controlling intermolecular carboacylation and hydroarylation of alkenes.

Highly enantioselective intramolecular cyanoamidation: (+)-horsfiline, (-)-coerulescine, and (-)-esermethole.

Insertion of an alkene into an ester: intramolecular oxyacylation reaction of alkenes through acyl C-O bond activation.

Concise synthesis of ω-borono-α-amino acids

RETRACTED: Catalytic C–CN activation and asymmetric cyanoamidation of alkenes: total syntheses of (+)-horsfiline, (−)-coerulescine, and (−)-esermethole