Asymmetric synthesis of metallocenes with planar and central chirality by rhodium-catalyzed desymmetrization reactions DOI Creative Commons

Nan‐Nan Hang,

En-Guang Tong,

Ting Qi

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Metallocenes with planar and central chirality have emerged as a privileged skeleton for chiral ligand design, such ligands exhibited tremendous success in various asymmetric catalysis protocols. Herein, we report rhodium/chiral diene-catalyzed desymmetrization of 1,2-diformylmetallocenes aryl/alkenylboronic acids to give enantio-enriched formylmetallocenes, which are diastereoisomers Ugi-type products. This catalytic system also enables the kinetic resolution 2-substituted 1-formylferrocene selectivity factor (s) up 4331. Compared traditional synthesis methods, our method has following advantages: (1) opposite diastereoselectivity; (2) synthesis; (3) single-step construction chirality. The synthetic utility present is demonstrated by series phosphine ligands, including Josiphos- PPFA-type ligands.

Language: Английский

Radical Reactions with N-Heterocyclic Carbene (NHC)-Derived Acyl Azoliums for Access to Multifunctionalized Ketones DOI

Hui Cai,

Xiaoqun Yang,

Shi‐Chao Ren

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8270 - 8293

Published: May 13, 2024

As one of the most important key intermediates, NHC-bound acylazolium-based ionic transformations have been intensively explored in past two decades. With expeditious development NHC-catalyzed radical recent years, acylazolium chemistry has reached another level, with number relevant publications increasing significantly. However, a summary focused on acylations NHC-derived acyl azoliums classified according to mechanistic difference not reported. Such detailed classification and deep analysis provide opportunities for better understanding history trend this field. In review, reactions N-heterocyclic carbene (NHC)-derived are systematically introduced. The achievements challenges within area also summarized discussed at end.

Language: Английский

Citations

23
Enantioselective Synthesis of C−O Axially Chiral Diaryl Ethers by NHC‐Catalyzed Atroposelective Desymmetrization** DOI
Sayan Shee,

Sowmya Shree Ranganathappa,

Mahesh S. Gadhave

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 21, 2023

Axially chiral diaryl ethers, a distinguished class of atropisomers possessing unique dual C-O axis, hold immense potential for diverse research domains. In contrast to the catalytic enantioselective synthesis conventional single axis bearing atropisomers, atroposelective axially ethers containing flexible remains significant challenge. Herein, we demonstrate first N-heterocyclic carbene (NHC)-catalyzed via esterification dialdehyde-containing ethers. Mechanistically, reaction proceeds NHC-catalyzed desymmetrization strategy afford corresponding ether in good yields and high enantioselectivities under mild conditions. The derivatization synthesized product expands utility present access library compounds. temperature dependency preliminary investigations on racemization barrier bonds are also presented.

Language: Английский

Citations

40
N-Heterocyclic carbene-catalyzed enantioselective (dynamic) kinetic resolutions and desymmetrizations DOI
Yi Zhang, Hui Cai, Xiuhai Gan

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(2), P. 482 - 511

Published: Sept. 11, 2023

Language: Английский

Citations

39
N-Heterocyclic Carbene-Catalyzed Atroposelective Synthesis of N–N Axially Chiral 3-Amino Quinazolinones DOI
Kuruva Balanna,

Soumen Barik,

Shilpa Barik

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8752 - 8759

Published: June 16, 2023

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C–C bonds is well-known, C–N bond-containing relatively less explored, construction N–N has received only scant attention. Demonstrated herein N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction, leading to 3-amino quinazolinones. The NHC-catalyzed reaction quinazolinones containing a free N–H moiety with α,β-unsaturated aldehydes under oxidative conditions furnished atropisomeric quinazolinone derivatives mild broad scope. Preliminary studies on experimental density functional theory-based rotational barrier determination are also presented.

Language: Английский

Citations

32
Synthesis of axially chiral diaryl ethers via NHC-catalyzed atroposelective esterification DOI Creative Commons

Yingtao Wu,

Xin Guan,

Huaqiu Zhao

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(12), P. 4564 - 4570

Published: Jan. 1, 2024

We present NHC-catalyzed atroposelective esterification of prochiral dialdehydes, delivering enantioenriched axially chiral diaryl ethers. Matched kinetic resolutions amplify the enantioselectivity by removing minor enantiomers via over-functionalization.

Language: Английский

Citations

16
N-Heterocyclic carbene-catalyzed enantioselective synthesis of planar-chiral cyclophanes via dynamic kinetic resolution DOI Creative Commons
Jiayan Li, Ziyang Dong, Chen Yang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 15, 2024

Abstract Planar-chiral cyclophanes have gained considerable concerns for drug discovery due to their unique conformational strain and 3D structure. However, the enantioselective synthesis of planar-chiral is a long-standing challenge synthetic community. We herein describe an N-heterocyclic carbene (NHC)-catalyzed asymmetric construction cyclophanes. This transformation occurs through dynamic kinetic resolution (DKR) process convert racemic substrates into macrocycle scaffolds in good high yields with excellent enantioselectivities. The ansa chain length aromatic ring substituent size crucial achieve DKR approach. Controlled experiments DFT calculations were performed clarify process.

Language: Английский

Citations

15
Atroposelective Synthesis of N–N Axially Chiral Indoles and Pyrroles via NHC-Catalyzed Diastereoselective (3 + 3) Annulation Strategy DOI

Sowmya Shree Ranganathappa,

Bhabani Sankar Dehury,

Gautam Kumar Singh

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6965 - 6972

Published: April 18, 2024

The synthesis of N–N axially chiral molecules in the enantiopure form has emerged as an interesting research topic primarily due to significance and intricacy synthesizing these molecules, especially bearing heterocyclic motifs. Herein, we disclose a method for introduction axial chirality along with point center via N-heterocyclic carbene (NHC)-catalyzed atroposelective dihydropyridinone-containing indoles pyrroles. reaction follows (3 + 3) annulation approach by interception indole/pyrrole-derived enamines α,β-unsaturated aldehydes under oxidative NHC catalysis proceeding acylazoliums. indoles/pyrroles were formed mild conditions broad scope high selectivity. In addition, preliminary DFT studies rotational barrier products performed.

Language: Английский

Citations

14
N-Heterocyclic Carbene-Catalyzed Highly Enantioselective Macrolactonization to Access Planar-Chiral Macrocycles DOI

Jiaming Wang,

Meng Wang,

Yilu Wen

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(5), P. 1040 - 1045

Published: Jan. 31, 2024

An N-heterocyclic carbene (NHC)-catalyzed atroposelective macrolactonization has been disclosed. This approach affords planar-chiral macrocycles in high yields with excellent enantioselectivities over a broad substrate scope. Controlled experiments suggest that the enantioselectivity might arise from cation–n interaction between acyl azolium and electron-rich moiety substrate. mechanism is supported by density functional theory calculations, which also an important π–π stabilizing transition state.

Language: Английский

Citations

12
Atroposelective Synthesis of Axially Chiral Diaryl Ethers by N-Heterocyclic-Carbene-Catalyzed Sequentially Desymmetric/Kinetic Resolution Process DOI
Libo Li,

Wenqing Ti,

Tianshu Miao

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 4067 - 4073

Published: Feb. 23, 2024

We describe herein an N-heterocyclic-carbene-catalyzed atroposelective synthesis of axially chiral diaryl ethers. Through a sequentially enantioselective desymmetric process and kinetic resolution process, the products could be constructed in good yields with excellent enantiopurities. Both alcohols phenols were compatible this catalytic system. The carboxylic acids derived from esters proven to potential ligands for asymmetric synthesis, example, Rh(III)-catalyzed C–H functionalization.

Language: Английский

Citations

10
Catalytic N-Acylation for Access to N–N Atropisomeric N-Aminoindoles: Choice of Acylation Reagents and Mechanistic Insights DOI

Chaoyang Song,

Pang Chen,

Youlin Deng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6926 - 6935

Published: April 18, 2024

The synthesis of N–N axial compounds containing aromatic acyl amides using common acylation reagents remains challenging. We describe a highly atropenantioselective N-aminoindoles axes. A chiral cyclic isothiourea is used as the sole organic catalyst in transformation N-acylation reaction. Aroyl chlorides have been to construct atropisomeric through N-acylation. N-aminoindole products, which bear stereogenic axes, were synthesized with high yields and enantioselectivities. Some enantiopure products exhibited promising antibacterial activities against plant pathogens.

Language: Английский

Citations

10