
Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(7), P. 100669 - 100669
Published: June 19, 2023
Language: Английский
Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(7), P. 100669 - 100669
Published: June 19, 2023
Language: Английский
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3812 - 3844
Published: Feb. 23, 2024
Chiral skeletons with multiple stereogenic centers widely reside in nature and drugs, their relative absolute configuration often determine physiological or pharmacological properties. Stereodivergent synthesis of chiral molecules is not only great significance, but also highly challenging since the formation one diastereomers inherently preferred most asymmetric reactions. dual catalysis, introduced 2013 by Carreira group, perfectly catered to all requirements for full stereoselectivity control given reactions two catalysts are utilized a synergistic way act independently, has now been arguably efficient strategy realize stereodivergent synthesis. This comprehensive review presents an overview development enabled catalysis past ten years, providing readers fundamental attributes as well ability, scope, mechanism, limitations this strategy.
Language: Английский
Citations
33Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9241 - 9251
Published: March 19, 2024
Much attention has been focused on the catalytic asymmetric creation of single chiral centers or two adjacent stereocenters. However, construction nonadjacent stereocenters is significant importance but challenging because lack remote induction models. Herein, based a C═C bond relay strategy, we report synergistic Pd/Cu-catalyzed 1,5-double model. All four stereoisomers target products bearing 1,5-nonadjacent involving both allenyl axial and central chirality could be obtained divergently by simply changing combination catalysts with different configurations. Control experiments DFT calculations reveal novel mechanism 1,5-oxidative addition, contra-thermodynamic η3-allyl palladium shift, conjugate nucleophilic substitution, which play crucial roles in control reactivity, regio-, enantio-, diastereoselectivity. It expected that this strategy may provide general protocol for synthesis structural motifs distant
Language: Английский
Citations
19Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)
Published: May 22, 2023
We herein describe an asymmetric α-allylic allenylation of β-ketocarbonyls and aldehydes with 1,3-enynes. A synergistic chiral primary amine/Pd catalyst was identified to facilitate the utilization 1,3-enynes as atom-economic achiral allene precursors. The catalysis enables construction all-carbon quaternary centers-tethered allenes bearing non-adjacent 1,3-axial central stereogenic centers in high level diastereo- enantio-selectivity. By switching configurations ligands aminocatalysts, diastereodivergence can be achieved any four diastereoisomers accessed enantio- selectivity.
Language: Английский
Citations
27Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3427 - 3437
Published: Jan. 20, 2024
Despite half a century's advance in the field of transition-metal-catalyzed asymmetric alkene hydrogenation, enantioselective hydrogenation purely alkyl-substituted 1,1-dialkylethenes has remained an unmet challenge. Herein, we describe chiral PCNOx-pincer iridium complex for transfer this class with ethanol, furnishing all-alkyl-substituted tertiary stereocenters. High levels enantioselectivity can be achieved reactions substrates secondary/primary and primary/primary alkyl combinations. The catalyst is further applied to redox isomerization disubstituted alkenols, producing stereocenter remote resulting carbonyl group. Mechanistic studies reveal dihydride species, (PCNOx)Ir(H)2, as catalytically active intermediate, which decay dimeric species (κ3-PCNOx)IrH(μ-H)2IrH(κ2-PCNOx) via ligand-remetalation pathway. deactivation under conditions H2 much faster than that EtOH, explains why (PCNOx)Ir effective but ineffective hydrogenation. suppression di-to-trisubstituted by regioselective 1,2-insertion partly responsible success system, underscoring critical role played pincer ligand 1,1-dialkylethenes. Moreover, computational elucidate significant influence London dispersion interaction between substrate on control, illustrated complete reversal stereochemistry through cyclohexyl-to-cyclopropyl group substitution substrates.
Language: Английский
Citations
12Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)
Published: Feb. 27, 2024
A novel enantioselective Tsuji-Trost-type cross coupling reaction between gem-difluorinated cyclopropanes and N-unprotected amino acid esters enabled by synergistic Pd/Ni/chiral aldehyde catalysis is presented herein. This transformation streamlined the diversity-oriented synthesis (DOS) of optically active α-quaternary α-amino bearing a linear 2-fluoroallylic motif, which served as an appealing platform for construction other valuable enantioenriched compounds. The key intermediates were confirmed HRMS detection, while DFT calculations revealed that excellent enantioselectivity was attributed to stabilizing non-covalent interactions Pd(II)-π-fluoroallyl species Ni(II)-Schiff base complex.
Language: Английский
Citations
12Advanced Science, Journal Year: 2024, Volume and Issue: 11(23)
Published: March 21, 2024
Abstract Asymmetric sequential hydrogenations of α ‐methylene γ ‐ or δ ‐keto carboxylic acids are established in one‐pot using a bimetallic Ru/Ru catalyst system, achieving the stereodivergent synthesis all four stereoisomers both chiral and ‐lactones with two non‐vicinal carbon stereocenters high yields (up to 99%) excellent stereoselectivities >99% ee >20:1 dr). The compatibility Ru systems is investigated detail, it found that basicity reaction system plays key role hydrogenation processes. protocol can be performed on gram‐scale low loading 11000 S/C) resulting products allow for many transformations, particularly several intermediates useful preparation drugs natural products.
Language: Английский
Citations
10JACS Au, Journal Year: 2023, Volume and Issue: 3(10), P. 2612 - 2630
Published: Sept. 26, 2023
Alongside enantioselective catalysis, synthetic chemists are often confronted by the challenge of achieving catalyst control over relative configuration to stereodivergently access desired diastereomers. Typically, these approaches iteratively or simultaneously multiple stereogenic units for which dual catalytic methods comprising sequential, relay, and synergistic catalysis emerged as particularly efficient strategies. In this Perspective, benefits challenges catalyst-controlled diastereodivergence in construction carbon stereocenters discussed on basis illustrative examples. The concepts then transferred diastereodivergent atropisomeric systems with twofold higher-order stereogenicity well E- Z-configured alkenes.
Language: Английский
Citations
21Chemical Science, Journal Year: 2023, Volume and Issue: 14(15), P. 4134 - 4142
Published: Jan. 1, 2023
Highly selective assembly of 2,3-fused indolizines was achieved via a cascade allylation/Friedel–Crafts type reaction with Cu/Ir catalysis. This protocol furnishes stereodivergent synthesis chiral bearing three stereogenic centers excellent results.
Language: Английский
Citations
20Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(8), P. 2238 - 2255
Published: July 20, 2023
Language: Английский
Citations
19Chemical Science, Journal Year: 2024, Volume and Issue: 15(22), P. 8280 - 8294
Published: Jan. 1, 2024
The synthesis of enantiomerically pure compounds is a pivotal subject in the field chemistry, with enantioselective catalysis currently standing as primary approach for delivering specific enantiomers. Among these strategies, Cu-catalyzed asymmetric allylic substitution (AAS) significant and irreplaceable, especially when it comes to use non-stabilized nucleophiles (pK > 25). Although AAS prochiral substrates has also been widely developed, methodologies involving racemic/meso are highly desirable, undergo dynamic processes give single enantiomer products. Inspired by pioneering work Alexakis, Feringa Gennari groups, continuously employed deracemization desymmetrization enriched In this review, we mainly focus on developments over past two decades, providing an explicit outline ligands employed, scope nucleophiles, underlying their practical applications.
Language: Английский
Citations
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