Enantioselective desymmetrization reactions in asymmetric catalysis

Tetrahedron, Journal Year: 2022, Volume and Issue: 106-107, P. 132629 - 132629

Published: Jan. 1, 2022

Language: Английский

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Magnesium Catalysis in Asymmetric Synthesis

Chem, Journal Year: 2019, Volume and Issue: 5(5), P. 1108 - 1166

Published: Feb. 28, 2019

Language: Английский

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Kinetic Resolution of trans-2,3-Aziridinyl Alcohols via Hydroxyl Directed Regio- and Enantioselective Ring Opening Reactions

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 6873 - 6878

Published: May 4, 2023

An efficient kinetic resolution of racemic trans-2,3-aziridinyl alcohols is established via zinc catalyzed ring opening reactions with various amines as the nucleophiles. The directing effect hydroxyl group and precise enantiodiscrimination by dinuclear cooperative catalyst are keys to success high regioselectivity enantioselectivity. A range enantioenriched vicinal diamines were obtained in good yields excellent ee values. To best our knowledge, this first example directed enantioselective nucleophilic 2,3-aziridinyl alcohols.

Language: Английский

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Catalytic Asymmetric [8+3] Annulation Reactions of Tropones or Azaheptafulvenes with meso‐Aziridines

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(51), P. 13428 - 13431

Published: July 11, 2018

Highly enantioselective [8+3] high-order cycloaddition reactions of tropones or azaheptafulvenes with meso-aziridines were achieved by a desymmetrization/annulation process in the presence chiral N,N'-dioxide/Mg(OTf)2 complex. The corresponding tetrahydrocyclohepta[b][1,4]oxazines and tetrahydro-1H-cyclohepta- [b]-pyrazines obtained good yields (66-98 %) excellent diastereo- enantioselectivities (>19:1 d.r., 90-96 % ee). A possible transition state model was proposed to elucidate origin induction based on control experiments X-ray crystal structure catalyst.

Language: Английский

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Divergent Synthesis of Enantioenriched β-Functional Amines via Desymmetrization of meso-Aziridines with Isocyanides

Organic Letters, Journal Year: 2019, Volume and Issue: 21(15), P. 6096 - 6101

Published: July 24, 2019

A highly enantioselective ring-opening desymmetrization of meso-aziridines with isocyanides was achieved in the presence a chiral N,N′-dioxide/Mg(OTf)2 complex. The situ generated 1,4-zwitterionic intermediates were successfully trapped by intramolecular oxygen- and carbon-based nucleophiles or exogenous H2O TMSN3, enabling collective synthesis various vicinal amino-oxazoles, spiroindolines, β-amino amides, tetrazole derivative moderate to high yields excellent enantioselectivities.

Language: Английский

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Catalytic asymmetric synthesis of 1,2-diamines

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(15), P. 7983 - 8085

Published: Jan. 1, 2024

The asymmetric catalytic synthesis of 1,2-diamines has received considerable interest, due to their presence in biologically active compounds and applications for the development synthetic building blocks, chiral ligands organocatalysts.

Language: Английский

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Regioselective, Lewis Acid-Catalyzed Ring-Openings of 2,3-Aziridyl Alcohols with Azoles

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Methods for regioselective ring-opening reactions of N-sulfonyl-protected aziridyl alcohols with azole nucleophiles have been developed. Several classes azoles, including indazole, substituted pyrazole, benzotriazole, and tetrazole, employed as reaction partners, giving rise to C3-selective opening >3:1 N-selectivity. BF3•OEt2 is the optimal catalyst most substrate combinations, although examples where diphenylborinic acid (Ph2BOH) provides higher yields, or proceed efficiently without a catalyst, are also described. Computational modeling BF3•OEt2-catalyzed consistent observed regiochemical outcome. The calculated transition state appears be stabilized by an unconventional OH···FB hydrogen-bonding interaction.

Language: Английский

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Stereoselective Synthesis of Hexahydroimidazo[1,2-a]quinolines via S_N2-Type Ring-Opening Hydroarylation–Hydroamination Cascade Cyclization of Activated Aziridines with N-Propargylanilines

Organic Letters, Journal Year: 2020, Volume and Issue: 22(20), P. 7903 - 7908

Published: Sept. 28, 2020

A novel synthetic approach for the construction of 1,2,3,3a,4,5-hexahydroimidazo[1,2-a]quinolines in good yields (up to 75%) with excellent stereoselectivity (dr up 94:6, ee >99%) under one-pot domino ring-opening cyclization (DROC) conditions has been developed. The DROC protocol proceeds through a Lewis acid catalyzed SN2-type activated aziridines N-propargylanilines followed by intramolecular comprising concomitant hydroarylation and hydroamination steps fashion.

Language: Английский

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Azole‐Directed Cobalt‐Catalyzed Asymmetric Hydrogenation of Alkenes

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(44)

Published: May 27, 2022

The azole-directed cobalt-catalyzed asymmetric hydrogenation of alkenes has been developed with high efficiency. With this approach, chiral pyrazole compounds were obtained in quantitative yields and excellent enantioselectivities (up to 99 % ee) under mild conditions, the was conducted on a gram scale up 2000 TON. Several useful applications demonstrated including convenient introduction β-chirality drug intermediate containing an azole ring.

Language: Английский

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Magnesium-catalyzed stereoselective transformations – A survey through recent achievements

Polyhedron, Journal Year: 2022, Volume and Issue: 219, P. 115790 - 115790

Published: March 23, 2022

Magnesium (Mg) constitutes one of the most abundant metal elements in Earth’s crust. The spectacular career magnesium organic chemistry has been initiated at beginning XX century and still lasting today. discovery organomagnesium compounds by Philippe A. Barbier Victor Grignard is commonly recognized as milestones development (organic) chemistry. subsequent applications reagents relatively easy generated synthons enantioselective reactions have opened new possibilities for acquiring enantiomerically enriched compounds. On other hand, asymmetric which plays a role catalyst can be considered limited, especially when their number compared to contributions aimed transition metal-catalyzed or organocatalyzed stereoselective transformations. However, taking into account current trends replacing expensive metals with cheaper counterparts making catalysis more environmentally (and user) friendly, modification known methods, employ Earth-abundant metals, very advisable. In this study we intend emphasize chemistry, mainly catalytic synthesis. Among already reported procedures, discussed recent examples, however, also mentioned some, groundbreaking previous ones. An exception pericyclic made, these constitute first examples use attention drawn some structural aspects, associated either experimentally-determined geometry species calculated state(s) given transformation.

Language: Английский

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