Diastereodivergence in catalytic asymmetric conjugate addition of carbon nucleophiles DOI
Byungjun Kim,

Hooseung Lee,

In‐Sun Song

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 11, 2024

Catalytic asymmetric conjugate additions of carbon nucleophiles have emerged as a potent tool for constructing multi-stereogenic molecules with precise stereochemical control. This review explores the concept diastereodivergence in such reactions, focusing on strategies to achieve selective access diverse diastereomeric products upon carbon-carbon bond formation. Drawing from rich array examples, we delve into key approaches controlling outcome these transformations, including alteration alkene geometry, fine-tuning reaction parameters, synergistic catalysis, and isomerization adducts. Additionally, highlight iterative additions, showcasing their potential diastereodivergent synthesis methyl-branched stereocenters 1,3-relationships. By presenting concentrated overview this significant topic, aims provide valuable insights design execution stereodivergent catalytic offering new avenues advancing stereoselective structural diversity organic synthesis.

Language: Английский

Diastereodivergent and Regioselective Synthesis of Tetrahydrofuro[2,3-b]furans with Four Consecutive Stereocenters DOI
Jing Zhang,

Wen‐Na Sun,

Zhiwei Jiang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4134 - 4144

Published: Feb. 23, 2024

Base-catalyzed diastereodivergent and regioselective domino processes of triketone enones with arylacetaldehydes for the synthesis tetrahydrofuro[2,3-

Language: Английский

Citations

1
Switchable Chemo‐, Regio‐ and Pseudo‐Stereodivergence in Palladium‐Catalyzed Cycloaddition of Allenes DOI

Pengfei Luo,

Jinxia Li, Yu‐Hua Deng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 11, 2024

Here, we report a strategy enabling triple switchable chemo-, regio-, and stereodivergence in newly developed palladium-catalyzed cycloadditions of allenes. An asymmetric pseudo-stereodivergent cycloaddition allenes bearing primary leaving group at the α-position, where dynamic kinetic hydroalkoxylation racemic unactivated was enantio-determining step, is realized, providing four stereoisomers [(Z,R), (Z,S), (E,S), (E,R)] containing di-substituted alkene scaffold stereogenic center. By tuning reaction conditions, mechanistically distinctive uncovered selectively with same set substrates. switching position allenes, involving an intermolecular O-attack disclosed. Diverse mechanisms reactions enable rapid access to structurally stereochemically diverse 3,4-dihydro-2H-1,4-benzoxazines high efficiency selectivity.

Language: Английский

Citations

1
Divergent asymmetric reactions of α-alkenyl ketones with β,γ-alkynyl-α-imino esters enabled by chiral phosphoric acids DOI Creative Commons
Guosong Shen,

Faqian He,

Xiaoyu Yang

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

1
Solvent-Controlled Diastereodivergent Synthesis of Hexahydropyrrolo[2,1-a]isoquinolines through Pd/C-Catalyzed Dehydrogenative [3 + 2] Cycloaddition DOI

Ji-Chao Lu,

Hao Bai,

Ying Huang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

A Pd/C-catalyzed dehydrogenative [3 + 2] cycloaddition is described for the diastereoswitchable synthesis of hexahydropyrrolo[2,1-a]isoquinolines by altering solvents. The reaction proceeds through a sequential formation azomethine ylides from tetrahydroisoquinoline acetates and 1,3-dipolar with 2-nitroethenylbenzenes. This method displayed tunable diastereoselectivity, broad substrate scope good functional group compatibility. Moreover, gram-scale selective reductive or oxidative transformations product further demonstrate utility this methodology.

Language: Английский

Citations

1
Stereodivergent synthesis of chiral spiropyrazolones through Pd-catalyzed asymmetric sequential hydroalkylation of 1,3-enynes: unusual solvent effects on the enantioselectivity DOI
Shan Wang,

Long Li,

Yifei Zheng

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(11), P. 3033 - 3040

Published: Jan. 1, 2024

Chiral spiropyrazolones were constructed through Pd-catalyzed asymmetric sequential hydroalkylation of 1,3-enynes. Four stereoisomers could be obtained substrate control and chiral ligand control.

Language: Английский

Citations

0
Reactivity and Steric Parameters from 2D to 3D Bulky Pyridines: Increasing Steric Demand at Nitrogen with Chiral Azatriptycenes DOI Creative Commons

Ali Ben Saida,

Damien Mahaut, Nikolay Tumanov

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(32)

Published: May 23, 2024

Abstract Sterically hindered pyridines embedded in a three‐dimensional triptycene framework have been synthesized, and their resolution by chiral HPLC enabled access to unprecedented enantiopure exceeding the known steric limits. The design principles for new axially pyridine derivatives are then described. To rationalize associations with Lewis acids transition metals, comprehensive determination of electronic parameters this class was performed. This led general parameterization (percent buried volume %V Bur , Tolman cone angle θ, He 8 _steric descriptor) large set two‐ derivatives. These shown describe quantitatively interactions carbon‐ boron‐centered were used predict ΔG° association prototypical B(C 6 F 5 ) 3 acid widely frustrated pair catalysis. first sterics is fundamental basis future development predictive reactivity models guiding applications bulky organocatalysis, pairs, transition‐metal

Language: Английский

Citations

0
Reactivity and Steric Parameters from 2D to 3D Bulky Pyridines: Increasing Steric Demand at Nitrogen with Chiral Azatriptycenes DOI Creative Commons

Ali Ben Saida,

Damien Mahaut, Nikolay Tumanov

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 23, 2024

Abstract Sterically hindered pyridines embedded in a three‐dimensional triptycene framework have been synthesized, and their resolution by chiral HPLC enabled access to unprecedented enantiopure exceeding the known steric limits. The design principles for new axially pyridine derivatives are then described. To rationalize associations with Lewis acids transition metals, comprehensive determination of electronic parameters this class was performed. This led general parameterization (percent buried volume %V Bur , Tolman cone angle θ, He 8 _steric descriptor) large set two‐ derivatives. These shown describe quantitatively interactions carbon‐ boron‐centered were used predict ΔG° association prototypical B(C 6 F 5 ) 3 acid widely frustrated pair catalysis. first sterics is fundamental basis future development predictive reactivity models guiding applications bulky organocatalysis, pairs, transition‐metal

Language: Английский

Citations

0
Switchable Chemo‐, Regio‐ and Pseudo‐Stereodivergence in Palladium‐Catalyzed Cycloaddition of Allenes DOI

Pengfei Luo,

Jinxia Li, Yu‐Hua Deng

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)

Published: July 11, 2024

Abstract Here, we report a strategy enabling triple switchable chemo‐, regio‐, and stereodivergence in newly developed palladium‐catalyzed cycloadditions of allenes. An asymmetric pseudo‐stereodivergent cycloaddition allenes bearing primary leaving group at the α ‐position, where dynamic kinetic hydroalkoxylation racemic unactivated was enantio‐determining step, is realized, providing four stereoisomers [( Z,R ), ( Z,S E,S E,R )] containing di‐substituted alkene scaffold stereogenic center. By tuning reaction conditions, mechanistically distinctive uncovered selectively with same set substrates. switching position allenes, involving an intermolecular O‐attack disclosed. Diverse mechanisms reactions enable rapid access to structurally stereochemically diverse 3,4‐dihydro‐2 H ‐1,4‐benzoxazines high efficiency selectivity.

Language: Английский

Citations

0
Stereodivergent Synthesis of Atropisomeric Indole-Fused δ-Lactams Bearing All-Carbon Quaternary Stereocenters via Cu-Catalyzed Desymmetric Arene Amidation DOI

Bo‐Han Zhu,

Yu-Jie Ye,

Guanzhi Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 16639 - 16648

Published: Oct. 28, 2024

Language: Английский

Citations

0
Stereodivergent Assembly of δ-Valerolactones with an Azaarene-Containing Quaternary Stereocenter Enabled by Cu/Ru Relay Catalysis DOI Creative Commons

Kui Tian,

Z.‐T. JIN,

Xin‐Lian Liu

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 3, 2024

Stereodivergent synthesis of chiral δ-valerolactones bearing a unique azaarene-containing α-quaternary and tertiary stereocenter was enabled by Cu/Ru relay catalysis via cascade borrowing hydrogen/Michael addition/lactonization protocol.

Language: Английский

Citations

0