P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

---

Manganese‐Catalyzed Asymmetric Hydrogenation of 3H‐Indoles

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(20)

Published: March 3, 2022

The asymmetric hydrogenation (AH) of 3H-indoles represents an ideal approach to the synthesis useful chiral indoline scaffolds. However, very few catalytic systems based on precious metals have been developed realize this challenging reaction. Herein, we report a Mn-catalyzed AH with excellent yields and enantioselectivities. kinetic resolution racemic by was also achieved high s-factors construct quaternary stereocenters. Many acid-sensitive functional groups, which cannot be tolerated when using state-of-the-art ruthenium catalyst, were compatible manganese catalysis. This new process expands scope transformation highlights uniqueness earth-abundant metal reaction could proceed catalyst loadings at parts per million (ppm) level exceptional turnover number 72 350. is highest value yet reported for metal-catalyzed

Language: Английский

---

Bulky P-stereogenic ligands. A success story in asymmetric catalysis

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 489, P. 215192 - 215192

Published: May 9, 2023

Since the development of BisP* ligand by Imamoto, P-stereogenic phosphines bearing a bulky tert-butyl group and smaller alkyl have demonstrated extraordinary proficiency in wide range asymmetric processes. Over time, this class ligands has brought about introduction more rigid backbones, three-hindered quadrant concept, substitution adamantyl. The methyl fragment also been introduced phosphino-oxazoline-type ligands, chemists industrial sector contributed to evolution reporting first successful Buchwald-type monophosphines for coupling reactions. present review covers synthesis applications that developed since advent late 1990s, with special emphasis on successfully applied catalysis.

Language: Английский

---

Cobalt-Catalyzed Enantioconvergent Hydrogenation of Minimally Functionalized Isomeric Olefins

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(38), P. 17359 - 17364

Published: Sept. 15, 2022

Investigation on asymmetric hydrogenation of olefins is great importance in both pharmaceutical molecule synthesis and chemical industry due to the high demand for enantiopure compounds. The established methods often require geometrically pure olefins. enantioconvergent reaction provided possibility access a single stereoisomer via E/Z-olefin mixtures; however, polar functional group next carbon-carbon double bond was usually necessary. Here, we reported cobalt-catalyzed readily available minimally functionalized mixtures. This strategy shows good tolerance provides an alternative means transformation. preliminary mechanistic studies indicated that isomerization key achieve convergent

Language: Английский

---

Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Dec. 12, 2022

Chiral α-substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, ligands. However, their catalytic asymmetric synthesis is still rare. Of the only hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth-abundant transition-metal nickel catalyzed affording corresponding chiral products with up to 99 % yield, 96 ee (enantiomeric excess) (99 ee, after recrystallization) 1000 S/C (substrate/catalyst); this also first study on of terminal olefins using a catalyst under hydrogen atmosphere. The mechanism was investigated via deuterium-labelling experiments calculations which indicate that two added atoms come from gas. Additionally, it believed reaction involves NiII rather than Ni0 cyclic process based weak attractive interactions between Ni olefin substrate.

Language: Английский

---

Transition-metal-free regioselective and stereoselective C(sp²)–C(sp³) coupling of enamides with ethers or alkanes via photoredox-catalyzed cross-dehydrogenative coupling reactions

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(10), P. 4004 - 4011

Published: Jan. 1, 2022

A regio- and stereoselective C(sp 2 )–C(sp 3 ) coupling of enamides with ethers or alkanes via photoredox-catalyzed cross-dehydrogenative reactions is developed under environmentally friendly conditions.

Language: Английский

---

Nickel-Catalyzed Asymmetric Hydrogenation of γ-Keto Acids, Esters, and Amides to Chiral γ-Lactones and γ-Hydroxy Acid Derivatives

Organic Letters, Journal Year: 2022, Volume and Issue: 24(14), P. 2722 - 2727

Published: April 1, 2022

A highly efficient asymmetric hydrogenation of a series γ-keto acid derivatives, including acids, esters, and amides, using Ni-(R,R)-QuinoxP* complex as the catalyst has been developed to afford chiral γ-hydroxy derivatives with excellent enantioselectivities, up 99.9% ee. This method provides not only an economical one-pot approach for synthesis γ-lactones but also access (S)-norfluoxetine, inhibitor neural serotonin reuptake essential intermediate pharmaceutical synthesis.

Language: Английский

---

Cobalt‐Catalyzed Enantioselective Hydrogenation of Trisubstituted Carbocyclic Olefins: An Access to Chiral Cyclic Amides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: Feb. 27, 2023

The enantioselective hydrogenation of cyclic enamides has been achieved using an earth-abundant cobalt-bisphosphine catalyst. Using CoCl2 /(S,S)-Ph-BPE, several trisubstituted carbocyclic were reduced with high activity and excellent enantioselectivity (up to 99 %) the corresponding saturated amides. methodology can be extended synthesis chiral amines by base hydrolysis products. Preliminary mechanistic investigations reveal presence a spin cobalt (II) species in catalytic cycle. We propose that carbon-carbon double bond proceeds via sigma-bond-metathesis pathway.

Language: Английский

---

Cobalt‐Catalyzed Efficient Convergent Asymmetric Hydrogenation of E/Z‐Enamides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 12, 2023

Using the diphosphine-cobalt-zinc catalytic system, an efficient asymmetric hydrogenation of internal simple enamides has been realized. In particular, Ph-BPE ligand can achieve convergent E/Z-substrates. High yields and excellent enantioselectivities were obtained for both acyclic cyclic bearing α-alkyl-β-aryl, α-aryl-β-aryl, α-aryl-β-alkyl substituents. Hydrogenated products be applied synthesis useful chiral drugs such as Arfromoterol, Rotigotine, Norsertraline. addition, reasonable mechanism stereocontrol mode are proposed based on DFT calculations.

Language: Английский

---

Synthesis and applications of high-performance P-chiral phosphine ligands

Proceedings of the Japan Academy Series B, Journal Year: 2021, Volume and Issue: 97(9), P. 520 - 542

Published: Nov. 10, 2021

Metal-catalyzed asymmetric synthesis is one of the most important methods for economical and environmentally benign production useful optically active compounds. The success transformations significantly dependent on structure electronic properties chiral ligands coordinating to center metals, hence development highly efficient ligands, especially phosphine has long been an research subject in this field. This review article describes applications P-chiral possessing centers at phosphorus atoms. Rationally designed are synthesized by use phosphine-boranes as intermediates. Conformationally rigid electron-rich exhibit excellent enantioselectivity high catalytic activity various transition-metal-catalyzed reactions. Recent mechanistic studies rhodium-catalyzed hydrogenation also described.

Language: Английский

---