Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(18), С. 3592 - 3596
Опубликована: Янв. 1, 2024
An efficient method for the synthesis of alkenylphosphine oxides via addition-elimination SPOs to ketones has been developed. The reaction exhibits good yields and compatibility. Several conversions have also proven value this method.
Язык: Английский
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)
Опубликована: Март 4, 2024
Abstract Dienes have been of great interest to synthetic chemists as valuable substrates due their abundance and ease synthesis. Their unique stereoelectronic properties enable broad reactivity with a wide range transition metals construct molecular complexity facilitating synthesis biologically active compounds. In addition, structural diene variation can result in substrate‐controlled reactions, providing mechanistic insights into selectivity patterns. The last decade has seen wealth new methodologies involving through the power metal catalysis. This review summarizes recent advances remaining opportunities for metal‐catalyzed transformations dienes.
Язык: Английский
Процитировано
24
Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 883 - 971
Опубликована: Дек. 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.
Язык: Английский
Процитировано
42
Accounts of Chemical Research, Год журнала: 2024, Номер unknown
Опубликована: Янв. 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.
Язык: Английский
Процитировано
16
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)
Опубликована: Март 21, 2024
Abstract The construction of two distal stereocenters through a single catalytic process is great interest in organic synthesis. While there are some successful reports regarding stereodivergent preparation 1,3‐ or 1,4‐stereocenters, the more challenged 1,5‐nonadjacent have never been achieved fashion. Herein we describe synergistic palladium/copper catalysis for 1,4‐difunctionalization reactions 1,3‐dienes, providing access to quaternary stereocenters. Because each catalysts separately controlled one newly formed stereocenters, synthesis all four diastereomers products could readily be simply by choosing an appropriate combination chiral catalysts. Experimental and computational studies supported mechanism involving Heck/Tsuji–Trost cascade reaction, origins stereoselectivity were elucidated.
Язык: Английский
Процитировано
14
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)
Опубликована: Май 16, 2024
Abstract The construction of chiral motifs containing nonadjacent stereocenters in an enantio‐ and diastereoselective manner has long been a challenging task synthetic chemistry, especially with respect to their stereodivergent synthesis. Herein, we describe protocol that enables the 1,5/1,7‐nonadjacent tetrasubstituted through Pd/Cu‐cocatalyzed Heck cascade reaction. Notably, C=C bond relay strategy involving shift π‐allyl palladium intermediate was successfully applied asymmetric 1,7‐nonadjacent stereocenters. current method allows for efficient preparation molecules bearing two privileged scaffolds, oxindoles non‐natural α‐amino acids, good functional group tolerance. full complement four stereoisomers products could be readily accessed by simple combination metal catalysts different enantiomers.
Язык: Английский
Процитировано
11
Chemistry - A European Journal, Год журнала: 2024, Номер 30(26)
Опубликована: Фев. 13, 2024
Abstract Transition–metal catalyzed tandem asymmetric reactions were powerful tools to access various chiral compounds. Many strategies have been developed for the coupling of 1,n‐dienes with aryl halides via a Heck/Tsuji–Trost process. However, control regio‐ and stereo‐chemistry remains challenging task. This minireview details recent advances in field by palladium complex, which opened new opportunities expanded our understanding this area research years.
Язык: Английский
Процитировано
8
ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 5305 - 5313
Опубликована: Март 26, 2024
Over the past few decades, Narasaka–Heck-type difunctionalization of tethered alkenes has emerged as a powerful strategy to produce heterocyclic scaffolds. However, asymmetric synthesis rarely been explored. Herein, we report robust palladium-catalyzed enantioselective Narasaka–Heck cyclization–Sonogashira reaction alkene-tethered oxime esters and terminal alkynes. By employing new Ming-Phos ligand, obtain high yields pyrrolines with quaternary stereocenter enantioselectivities under mild conditions. Density functional theory (DFT) study reveals weak interaction between aromatic ring substrate fragment naphthyl group in which probably accounts for stereoselectivity.
Язык: Английский
Процитировано
7
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Янв. 10, 2025
The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity C–N bond cleavage. In study, we report nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled aziridines. Various types aziridines, including 2-phenyl, 2-carbonyl, 2-alkyl, and disubstituted consistently cleave their more sterically hindered bonds to generate 1,3-radical anion intermediates. These intermediates participate highly regioselective 1,4-Heck/allylic substitution cascade aromatic branched 1,3-dienes, resulting radical-polar crossover (4 + 3) produces seven-membered azepine products. This approach not only complements traditional dipolar cycloaddition, which typically act as zwitterionic 1,3-dipoles, but also introduces an unusual mode 1,3-dienes. Experimental investigations density functional theory (DFT) calculations provide insight into reaction mechanism.
Язык: Английский
Процитировано
1
RSC Advances, Год журнала: 2024, Номер 14(21), С. 14539 - 14581
Опубликована: Янв. 1, 2024
The synthesis of dihydrobenzofuran scaffolds bears pivotal significance in the field medicinal chemistry and organic synthesis. These heterocyclic hold immense prospects owing to their significant pharmaceutical applications as they are extensively employed essential precursors for constructing complex frameworks. Their versatility importance make them an interesting subject study researchers scientific community. While exploring synthesis, have unveiled various novel efficient pathways assembling core. In wake extensive data being continuously reported each year, we outlined recent updates (post 2020) on methodological accomplishments employing catalytic role several transition metals forge functionalities.
Язык: Английский
Процитировано
6
Advanced Science, Год журнала: 2024, Номер 11(31)
Опубликована: Июнь 17, 2024
Abstract Oxazocines are key structural intermediates in the synthesis of natural products and pharmaceutical molecules. However, oxazocines especially a highly enantioselective manner, is long‐standing formidable challenge due to unfavorable energetics involved cyclization. Herein, series new PNP‐Ligand P ‐chiral stereocenter first designed synthesized, called MQ‐Phos , successfully applied it Pd‐catalyzed higher‐order formal [4+4]‐cycloaddition α β ‐unsaturated imines with 2‐(hydroxymethyl)‐1‐arylallyl carbonates. The reaction features mild conditions, excellent regio‐ enantiocontrol broad substrate scope (54 examples). Various medium‐sized rings can be afforded moderate yields (up 92%) enantioselectivity 99% ee). newly developed critical for ring catalytic reactivity enantioselectivity.
Язык: Английский
Процитировано
6