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

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Recent advances in Pd-catalyzed asymmetric cyclization reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 883 - 971

Published: Dec. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Language: Английский

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 31, 2024

ConspectusPalladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted attention organic chemists. With development chiral ligands, increasingly challenging reactions and substantial progress catalysis are being realized.Since 2014, we have focused on exploiting a series sulfinamide phosphine ligands called "Sadphos," including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, WJ-Phos. These can be easily prepared two to four steps using commercial materials. new types shown remarkable performance transition-metal-catalyzed reactions, especially Pd-catalyzed transformations. X-ray diffraction analysis, mechanistic studies, density functional theory calculations revealed that Sadphos coordinate with Pd0 PdII species Pd0/P, Pd0/P,S, or PdII/P,O modes.This Account summarizes our recent efforts toward palladium-catalyzed enantioselective ligands. were found privileged very crucial promote by increasing reactivity enantioselectivity. Ming-Phos is an effective ligand coupling intramolecular Heck providing highly trisubstituted allenes, axially anilides, gem-diarylmethine silanes, disubstituted dihydroisoquinolinones. Incorporation electron-rich cyclohexyl group moiety afforded which showed unique effect transformations, reductive Heck, dearomative Mizoroki–Heck, tandem Heck/Suzuki coupling, carboiodination, carboamination, cross-coupling reactions. Using similar strategy, synthesized more electron–rich TY-Phos Xiang-Phos bearing t-butyl 1-adamantyl at P atoms, respectively. Regarding stereoelectronic features, these characteristic best choice satisfy requirements fluoroarylation gem-difluoroalkenes, intermolecular α-arylation aldehydes, carboetherification alkenyl oximes, carboheterofunctionalization 2,3-dihydrofurans. Compared aforementioned attractive features high nucleophilicity originating from CH2PPh2 ortho-substituent side aryl ring, presumably responsible for its efficiency. The Pd/Xiao-Phos catalyst system shows good secondary oxides, affording P-stereogenic products multiple molecular skeletons. modification basic backbone introducing xanthene skeleton motivated us design synthesize monophosphines, named PC-Phos GF-Phos. various arylation sulfenate anions, denitrogenative cyclization benzotriazoles, dearomatization indoles. practicability GF-Phos was validated three-component N-tosylhydrazones, halides, terminal alkynes, well N-tosylhydrazones vinyl iodides pendent amines. In addition, ferrocene-derived WJ-Phos employed Suzuki–Miyaura reaction, biaryl monophosphine oxides excellent enantiomeric excesses.

Language: Английский

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Catalytic Asymmetric Synthesis of Tröger’s Base Analogues with Nitrogen Stereocenter

ACS Central Science, Journal Year: 2023, Volume and Issue: 9(1), P. 64 - 71

Published: Jan. 4, 2023

Nitrogen stereocenters are common chiral units in natural products, pharmaceuticals, and catalysts. However, their research has lagged largely behind, compared with carbon other heteroatom stereocenters. Herein, we report an efficient method for the catalytic asymmetric synthesis of Tröger's base analogues nitrogen via palladium catalysis home-developed GF-Phos. It allows rapid construction a new rigid cleft-like structure both C- N-stereogenic center high efficiency selectivity. A variety applications as organocatalyst metallic catalyst precursors were demonstrated. Furthermore, DFT calculations suggest that NH···O hydrogen bonding weak interaction between substrate ligand crucial excellent enantioselectivity control.

Language: Английский

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Catalysis and Synthesis Enabled by P-Chiral Dihydrobenzooxaphosphole Ligands

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 949 - 977

Published: April 8, 2024

P-Chiral phosphorus ligands received little attention in organic chemistry until Knowles made his landmark contribution asymmetric hydrogenation by developing the P-chiral CAMP and DIPAMP. The development of accelerated end last century with advent some highly efficient renowned for hydrogenation, including BisP*, TangPhos, QuinoxP*, DuanPhos, et al. However, most reported were air-sensitive, difficult to make, or lacked structural modularity, hampering their availability applicability. sterically electronically tunable is particularly desirable. Over past decade, a family hindered, electron-rich, structurally tunable, air-stable dihydrobenzooxaphosphole emerged that proved be versatile various transformations. 5 years witnessed an increasing number studies related these discovery unprecedented catalytic properties This review highlights unique catalysis applications synthesis natural products therapeutic agents.

Language: Английский

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Ligand-enabled palladium-catalysed enantioselective synthesis of α-quaternary amino and glycolic acids derivatives

Nature Synthesis, Journal Year: 2023, Volume and Issue: 3(3), P. 357 - 367

Published: Dec. 4, 2023

Language: Английский

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Rhodium-Catalyzed Highly Enantio- and Diastereoselective Alkenylation of β,γ-Unsaturated Butenolides via Dynamic Kinetic Resolution

Organic Letters, Journal Year: 2022, Volume and Issue: 24(48), P. 8816 - 8820

Published: Nov. 30, 2022

A rhodium-catalyzed highly enantio- and diastereoselective alkenylation of β,γ-unsaturated butenolides is reported. The use a chiral diene ligand, (S,S)-Ph-bod, enables the facile synthesis butyrolactones in high yields with extremely enantioselectivities (>99% ee all cases) diastereoselectivities (up to >20:1 dr). key process reaction involves isomerization racemic α,β-unsaturated subsequent dynamic kinetic resolution through ligand-controlled, enantioselective an alkenylrhodium species that generated situ via 1,4-rhodium migration.

Language: Английский

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Palladium-Catalyzed γ-C–H Arylation of Unsaturated Carbonyl Compounds: An Emerging Remote Buchwald–Hartwig–Miura Arylation

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: July 30, 2024

Abstract As an important complement to the Buchwald–Hartwig–Miura arylation, Pd-catalyzed γ-C–H arylations, including γ-C(sp3)–H and γ-C(sp2)–H provide a more direct route install aryl group on less reactive γ-site of unsaturated carbonyl compounds, have attracted considerable interest from chemistry community in recent years. This review summarizes applications this method with both cyclic linear compounds (aldehydes, ketones, esters, amide, nitriles), as well total synthesis natural products (NPs), product skeletons, bioactive analogues. 1 Introduction 2 Arylation Cyclic Unsaturated Carbonyl Substrates 2.1 Exocyclic γ-Arylation 2.1.1 Ketones Corresponding Silyl-Dienol Ethers 2.1.2 Lactones 2.2 Endocyclic 2.2.1 2.2.2 2.2.3 Nitriles 3 Linear 3.1 Aldehydes 3.2 3.3 Amides 3.4 3.5 Silyl Ketene Acetals α,β-Unsaturated Esters 4 Conclusion

Language: Английский

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Amide‐Based Morita–Baylis–Hillman Carbonates for Phosphine‐Catalyzed Asymmetric (4+2) Annulation^†

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(24), P. 3269 - 3277

Published: Aug. 26, 2024

Comprehensive Summary Chiral phosphine‐catalyzed asymmetric (4+2) annulation of the amide‐based Morita–Baylis–Hillman (MBH) carbonates with β,γ‐unsaturated butenolides has been developed to give enantiomer‐enriched bicyclic δ‐lactam γ‐butyrolactone compounds. The MBH were first used as acceptor and aza‐C4 synthon in phosphine catalysis. Under mild reaction conditions, a variety unsaturated well tolerated provide chiral derivatives high yields excellent enantioselectivities diastereoselectivities. A plausible mechanism was also proposed based on control experiments DFT calculations.

Language: Английский

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Copper(I)‐Catalyzed Asymmetric Allylation of Ketones with 2‐Aza‐1,4‐Dienes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 13, 2023

Abstract Catalytic asymmetric allylation of ketones under proton‐transfer conditions is a challenging issue due to the limited pronucleophiles and electrophilic inertness ketones. Herein, copper(I)‐catalyzed with 2‐aza‐1,4‐dienes ( N ‐allyl‐1,1‐diphenylmethanimines) disclosed, which affords series functionalized homoallyl tertiary alcohols in high excellent enantioselectivity. Interestingly, ‐allyl‐1,1‐diphenylmethanimines work as synthetic equivalents propanals. Upon acidic workup, formal β‐addition propanals achieved. An investigation on KIE effect indicates that deprotonation rate‐determining step, generates nucleophilic allyl copper(I) species. Finally, utility present method demonstrated by synthesis R )‐boivinianin A )‐gossonorol.

Language: Английский

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