Iridium-Catalyzed Regiodivergent Atroposelective C–H Alkylation of Heterobiaryls with Alkenes DOI

Maoqian Xiong,

Zilong Yan,

Si‐Cong Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7243 - 7255

Published: April 24, 2024

The atroposelective direct C–H alkylation of heterobiaryls with simple alkenes represents a challenging and underexplored frontier. Herein we report an iridium(I)-catalyzed regiodivergent enantioselective 1-arylisoquinolines or 2-arylpyridines alkenes. By utilizing cationic iridium catalyst different types chiral bidentate phosphine ligands, both linear- branched-selective alkylations were achieved high regioselectivities enantioselectivities. With this atom-economic ligand-enabled protocol, series axially nitrogen-containing synthesized good efficiency enantioselectivity. For the linear-selective involving styrene moiety, computational investigations illuminated that regioselectivity is established during migratory insertion step into Ir–C bond. Both experimental density functional theory (DFT) studies concerning substituent effects moiety also conducted. These results suggest primacy role resonance effect relative to field-inductive in determining transformation.

Language: Английский

Data-driven design of new chiral carboxylic acid for construction of indoles with C-central and C–N axial chirality via cobalt catalysis DOI Creative Commons
Zijing Zhang, Shuwen Li, João C. A. Oliveira

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 31, 2023

Challenging enantio- and diastereoselective cobalt-catalyzed C-H alkylation has been realized by an innovative data-driven knowledge transfer strategy. Harnessing the statistics of a related transformation as source, designed machine learning (ML) model took advantage delta enabled accurate extrapolative enantioselectivity predictions. Powered model, virtual screening broad scope 360 chiral carboxylic acids led to discovery new catalyst featuring intriguing furyl moiety. Further experiments verified that predicted acid can achieve excellent stereochemical control for target alkylation, which supported expedient synthesis large library substituted indoles with C-central C-N axial chirality. The reported approach provides powerful data engine accelerate molecular catalysis harnessing hidden value available structure-performance statistics.

Language: Английский

Citations

32
Synthesis of Axially Chiral Biaryls through Cobalt(II)‐Catalyzed Atroposelective C−H Arylation DOI

Yong‐Jie Wu,

Zhen‐Kai Wang,

Zhen‐Sheng Jia

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward sustainable access to broad range enantioenriched biaryl-2-amines in good yields (up 99 %) with excellent enantioselectivities % ee). The synthetic utility the unprecedented method is highlighted by its scalability diverse transformations.

Language: Английский

Citations

31
Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions DOI
Zhuo‐Zhuo Zhang, Gang Zhou, Qiang Yue

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

Citations

16
Enantioselective C–H bond functionalization under Co(iii)-catalysis DOI

Bholanath Garai,

Abir Das,

Doppalapudi Vineet Kumar

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(25), P. 3354 - 3369

Published: Jan. 1, 2024

Enantioselective C–H functionalization relies on 4d and 5d metals, but with their depletion, sustainable alternatives using 3d metals are crucial.

Language: Английский

Citations

14
Iridium-Catalyzed Regiodivergent Atroposelective C–H Alkylation of Heterobiaryls with Alkenes DOI

Maoqian Xiong,

Zilong Yan,

Si‐Cong Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7243 - 7255

Published: April 24, 2024

The atroposelective direct C–H alkylation of heterobiaryls with simple alkenes represents a challenging and underexplored frontier. Herein we report an iridium(I)-catalyzed regiodivergent enantioselective 1-arylisoquinolines or 2-arylpyridines alkenes. By utilizing cationic iridium catalyst different types chiral bidentate phosphine ligands, both linear- branched-selective alkylations were achieved high regioselectivities enantioselectivities. With this atom-economic ligand-enabled protocol, series axially nitrogen-containing synthesized good efficiency enantioselectivity. For the linear-selective involving styrene moiety, computational investigations illuminated that regioselectivity is established during migratory insertion step into Ir–C bond. Both experimental density functional theory (DFT) studies concerning substituent effects moiety also conducted. These results suggest primacy role resonance effect relative to field-inductive in determining transformation.

Language: Английский

Citations

11