Enantio- and Diastereodivergent Construction of 1,3-Nonadjacent Stereocenters Bearing Axial and Central Chirality through Synergistic Pd/Cu Catalysis

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(32), P. 12622 - 12632

Published: Aug. 5, 2021

In contrast to the widely explored methods for asymmetric synthesis of molecules bearing a single stereocenter or adjacent stereocenters, concurrent construction 1,3-stereogenic centers in an enantio- and diastereoselective manner remains challenge, especially acyclic systems. Herein, we report diastereodivergent 1,3-nonadjacent stereocenters allenyl axial central chirality through synergistic Pd/Cu-catalyzed dynamic kinetic allenylation with racemic allenylic esters. The protocol is suitable wide range substrates including challenging esters less sterically bulky substituents provided chiral products high levels diastereoselectivities (up >20:1 dr >99% ee). Furthermore, several representative transformations involving axial-to-central transfer were conducted, affording useful structural motifs containing nonadjacent manner.

Language: Английский

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Copper-Catalyzed Enantioselective Radical 1,4-Difunctionalization of 1,3-Enynes

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(42), P. 18014 - 18021

Published: Oct. 9, 2020

Chiral allenes are important structural motifs frequently found in natural products, pharmaceuticals, and other organic compounds. Asymmetric 1,4-difunctionalization of 1,3-enynes is a promising strategy to construct axial chirality produce substituted chiral from achiral substrates. However, the previous state art focused on allenyl anion pathway. Because this, only electrophiles can be introduced into allene backbones second functionalization step, consequently limiting reaction product types. The development asymmetric via radical pathway would complement methods support expansion toolbox for synthesis allenes. Herein, we report first enantioselective formation group transfer context copper-catalyzed 1,3-enynes. This method addresses longstanding unsolved problem chemistry, provides an stereocontrol with free radicals, offers novel approach valuable, but previously inaccessible, work should shed light reactions may lead reactions.

Language: Английский

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Pd-Catalyzed Enantioselective Syntheses of Trisubstituted Allenes via Coupling of Propargylic Benzoates with Organoboronic Acids

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(21), P. 9763 - 9771

Published: April 25, 2020

Enabled by the newly developed ligand, Ming-Phos, first example of palladium-catalyzed highly enantioselective coupling racemic propargylic benzoates with organoboronic acids for chiral allenes synthesis has been developed. Excellent asymmetric induction achieved a decent substrate scope. Synthetic potentials construction polycyclic compounds multiple centers have demonstrated.

Language: Английский

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Recent Advances of Catalytic Enantioselective Heck Reactions and Reductive‐Heck Reactions

Chinese Journal of Chemistry, Journal Year: 2020, Volume and Issue: 39(3), P. 710 - 728

Published: Oct. 23, 2020

Abstract Heck reaction is one of the most important carbon‐carbon bond forming reactions with wide applications in organic synthesis. Considerable advances enantioselective have been achieved past decades. This review focuses on recent development catalytic asymmetric and reductive reaction, which covers intermolecular intramolecular versions since 2011. The article organized terms catalysts olefin substrates.

Language: Английский

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Design and Synthesis of TY‐Phos and Application in Palladium‐Catalyzed Enantioselective Fluoroarylation ofgem‐Difluoroalkenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(51), P. 22957 - 22962

Published: Sept. 25, 2020

Abstract The first example of highly enantioselective fluoroarylation gem‐difluoroalkenes with aryl halides is presented by using a new chiral sulfinamide phosphine ( Sadphos ) type ligand TY‐Phos . N‐Me‐ can be easily synthesized on gram scale from readily available starting materials in three steps. Salient features this work including materials, good yields, high enantioselectivities as well broad substrate scope make approach very practical and attractive. Notably, the asymmetric synthesis an analogue biologically active molecule also reported.

Language: Английский

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Enantioselective Copper-Catalyzed Radical Cyanation of Propargylic C–H Bonds: Easy Access to Chiral Allenyl Nitriles

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(36), P. 14451 - 14457

Published: Sept. 3, 2021

The first enantioselective copper-catalyzed cyanation of propargylic C–H bonds via radical relay was established using novel BoxOTMS ligands, providing an efficient and straightforward tool for the construction structurally diverse chiral allenyl nitriles in good yields with excellent enantioselectivities. This reaction features high functional group tolerance mild conditions. In addition, allene products can be readily converted to other compounds axis-to-center chirality transfer.

Language: Английский

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Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 446, P. 214120 - 214120

Published: July 19, 2021

The success of phosphine-oxazoline ligands (PHOX) inspired the progress in P-oxazoline ligand families by modifying either backbone, electronic and/or steric properties phosphine group or exchanging to a phosphinite phosphite group. In this respect, structures chiral have become more diverse and new very efficient emerged, which improved catalytic performance some asymmetric transformations, with an increased versatility, both range reactions substrates/reagents. addition, most are synthesized from easily accessible amino alcohols, maintaining short synthetic route developed for PHOX ligands. New been replacing oxazoline functionality several other N-donor groups, e.g. imidazole, thiazole, oxazole, pyridine, etc., O- S-groups. This review offers critical overview utility these successful bidentate heterodonor P-N, P-O P-S applied metal-mediated processes. We illustrate how, through proper design, can be excellent source ligands, superior many than best C2-symmetric N,N P,P-ligands reported so far.

Language: Английский

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Palladium/TY-Phos-Catalyzed Asymmetric Heck/Tsuji–Trost Reaction of o-Bromophenols with 1,3-Dienes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(8), P. 4378 - 4383

Published: Feb. 16, 2023

2,3-Dihydrobenzofurans are crucial building blocks in the synthesis of natural products and pharmaceutical molecules. However, their asymmetric has been a long-standing formidable challenge so far. In this work, we developed highly enantioselective Pd/TY-Phos-catalyzed Heck/Tsuji-Trost reaction o-bromophenols with various 1,3-dienes, allowing expedient access to chiral substituted 2,3-dihydrobenzofurans. This features excellent regio- enantiocontrol, high functional group tolerance, easy scalability. More importantly, demonstration method as valuable tool for construction optically pure (R)-tremetone fomannoxin is highlighted.

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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Diastereo‐ and Enantioselective 1,4‐Difunctionalization of Borylenynes by Catalytic Conjunctive Cross‐Coupling

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(26), P. 10311 - 10315

Published: March 25, 2020

Enantioselective conjunctive cross-coupling of enyne-derived boronate complexes occurs with 1,4 addition the electrophile and migrating group across π system. This reaction pathway furnishes α-boryl allenes as product. In presence a chiral catalyst, both central axial chirality product can be controlled during formation.

Language: Английский

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