Intermolecular Asymmetric Arylative Dearomatization of 1-Naphthols DOI Creative Commons

Max Kadarauch,

Tom Moss, Robert J. Phipps

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 4, 2024

Arylative dearomatization forms quaternary stereocenters in cyclic systems with the concomitant introduction of an aromatic ring. Pd-catalyzed arylative dearomatization, which uses conditions analogous to cross-coupling, has emerged as a powerful method intramolecular context. But translating this from cyclizations intermolecular process proven extremely challenging: examples are scarce, and those that exist have not been rendered enantioselective, despite potential for broad application medicinal chemistry natural product synthesis. We describe strategy utilizes attractive interactions between ligand substrate overcome challenge promote intermolecular, highly enantioselective naphthols using range aryl bromide electrophiles. Crucial success is use readily accessed sulfonated chiral phosphine sSPhos, we believe engages electrostatic substrate. Not only does sSPhos control enantioselectivity but it also drastically accelerates reaction, most likely by facilitating challenging palladation step initiates dearomatization.

Язык: Английский

Enantioselective Construction of Quaternary Stereocenters via Cooperative Photoredox/Fe/Chiral Primary Amine Triple Catalysis DOI
Lianjie Li,

J.Z.H. Zhang,

W. Li

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9404 - 9412

Опубликована: Март 20, 2024

The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable potentially versatile approach is coupling C–C bond through an outer-sphere mechanism, accompanied realization enantiocontrol cooperative catalysis; however, examples such processes are yet be identified. Herein, we present method for creating different compounds with photoredox/Fe/chiral primary amine triple catalysis. This facilitates connection unactivated alkyl source tertiary moiety, which also rare. scalable process exhibits mild conditions, does not necessitate use base, possesses good functional-group tolerance. Preliminary investigations into underlying mechanisms have provided valuable insights reaction pathway.

Язык: Английский

Процитировано

13
Inherently chiral resorcinarene cavitands through ionic catalyst-controlled cross-coupling DOI Creative Commons
Mingfeng Li,

Clement Kim Soon Ho,

Ivan Keng Wee On

и другие.

Chem, Год журнала: 2024, Номер 10(11), С. 3323 - 3341

Опубликована: Июль 5, 2024

Cavitands have emerged as privileged architectures in supramolecular chemistry. Nonetheless, achieving structural diversity and tunability through heterofunctionalization along the rims of macrocycles has remained a formidable challenge. As rudimental example, stepwise conversion C4v-symmetric scaffolds to inherently chiral ABCD patterns is synthetically impractical owing low theoretical yields (0.8%) need for chromatographic enantioseparation.Herein, we report catalytic desymmetrization strategy access cavitands. Through engineering ionic palladium catalysts, diverse functionalities, including aryl, alkenyl, alkynyl, amino groups, can be installed on large with high site- stereoselectivity. An adaptable protocol been established furnish designer ABCD-type cavitands accordance choreography coupling partners. Experimental computational studies reveal synergistic electrostatic steering catalysis by catalyst–substrate interactions.

Язык: Английский

Процитировано

5
ortho‐Selective Suzuki Coupling of Dichlorophenol and Dichlorobenzylalcohol in Water under Palladium Catalysis Directed by Noncovalent Interactions and Computational Analysis DOI Open Access

Shangxun Zhao,

Shuo Wen,

H Chen

и другие.

Asian Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 14, 2025

Abstract The use of attractive noncovalent interactions is emerging as a versatile approach to address site‐selectivity challenges. Herein, we report ortho‐selective Suzuki coupling reactions in water 2,3‐dichloroarenes and 2,4‐dichloroarenes bearing hydroxy group the presence palladacycle catalyst directed by interactions. Various ortho‐substituted arylphenols arylbenzyl alcohols were obtained good excellent yields with high selectivity. Density functional theory (DFT) calculations ab initio molecular dynamics (AIMD) simulations suggested that ortho ‐selective dichlorophenols dichlorobenzyl occurred through electrostatic hydrogen bonding interactions, respectively.

Язык: Английский

Процитировано

0
Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis DOI Creative Commons
Harry Adams,

Max Kadarauch,

Nicholas J. Hodson

и другие.

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Язык: Английский

Процитировано

0
Spokewise Total Syntheses of Four Erythrina Alkaloids and Telescoped Syntheses of Six Additional Alkaloids DOI

Yue‐Hong Hu,

Zhang‐Yan Gan,

Qin-Tong Li

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Based on rich sulfur-involving chemical transformations, a novel spokewise synthetic strategy, subclass of the collective strategies, has been developed to concisely synthesize four erythrina alkaloids through single-step transformation from common precursor. Moreover, six additional have also synthesized by subsequent 1-2 steps transformations. The current approaches provide valuable platform for total syntheses and

Язык: Английский

Процитировано

3
Synthesis of 3’H-Spiro[cyclohexane-1,1’-isobenzofuran]-2,5-dien-4- one and Skeleton Construction of Type D Spirobisnaphthalene Structure via Dearomatization by Highvalance Iodine Reagent and Diels-Alder Reaction DOI
Haoyun Ma, Xinkun An, Tingting Zhang

и другие.

New Journal of Chemistry, Год журнала: 2024, Номер 48(36), С. 15846 - 15855

Опубликована: Янв. 1, 2024

The core skeleton syntheses of 3′ H -spiro[cyclohexane-1,1′-isobenzofuran]-2,5-dien-4-one 3 were explored. Then, two key molecules (5ah and 6d) successfully constructed in 78% 39% overall yields.

Язык: Английский

Процитировано

1
Chiral Biaryl N-Heterocyclic Carbene–Palladium Catalysts with Anagostic C–H···Pd Interaction for Enantioselective Desymmetric C–N Cross-Coupling DOI
Woosong Han, Huijeong Ryu, Changmuk Kang

и другие.

Organic Letters, Год журнала: 2024, Номер 26(46), С. 9891 - 9896

Опубликована: Ноя. 11, 2024

Novel chiral biaryl imidazo[1,5-

Процитировано

1
Substrate NOBINAc ligand affinity for PdII-catalyzed enantioselective C–H activation over reactive β-C–H bonds in ferrocenyl amines DOI Creative Commons
Devendra Parganiha, Raviraj Ananda Thorat, Ashwini Dilip Dhumale

и другие.

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Дек. 13, 2024

Ferrocenyl amines as directing groups for C–H activation have limitations they are prone to undergo oxidation, allylic deamination, and β-hydride elimination.

Язык: Английский

Процитировано

1
Application of sSPhos as a Chiral Ligand for Palladium-Catalyzed Asymmetric Allylic Alkylation DOI Creative Commons

Philip J. Docherty,

Max Kadarauch,

Nisha Mistry

и другие.

Organic Letters, Год журнала: 2023, Номер 26(14), С. 2862 - 2866

Опубликована: Дек. 26, 2023

Palladium-catalyzed asymmetric allylic alkylation is a versatile method for C–C bond formation. Many established classes of chiral ligands can perform reactions enantioselectively, but identification new ligand remains important future development the field. We demonstrate that enantiopure sSPhos, bifunctional monophosphine ligand, when used as its tetrabutyl ammonium salt, highly effective benchmark Pd-catalyzed reaction. explore scope and limitations experiments to probe origin selectivity. In contrast with previously explored using it appears steric bulk around sulfonate group responsible high enantioselectivity in this case, rather than attractive noncovalent interactions.

Язык: Английский

Процитировано

3
Organocatalytic Dearomative Spirocyclization Reaction of Enone-Tethered α-and β-Naphthols and Dearomatization Reaction of In Situ Generated Nitro-Olefin-Tethered α-Naphthols DOI

Amit Shikari,

Madhur Sharma,

Kalishankar Bhattacharyya

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 9769 - 9782

Опубликована: Июнь 26, 2024

Herein, we report a catalytic dearomative spirocyclization reaction of new substrates having aryl/alkyl enone tethered α- and β-naphthols dearomatization in situ generated nitro-olefin-tethered α-naphthols. The spirocarbocycles were obtained moderate to good yields with high diastereoselectivities. A preliminary asymmetric variant was reported. few applications such as hydrogenations epoxidation have also been demonstrated. Theoretical study has performed understand diastereoselectivity the triethylamine catalyzed reaction.

Язык: Английский

Процитировано

0