Unsymmetric N-heterocyclic carbene ligand enabled nickel-catalysed arylation of bulky primary and secondary amines DOI Creative Commons
Zi-Chao Wang, Yanyu Li, Shuo‐Qing Zhang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(16), P. 4390 - 4396

Published: Jan. 1, 2023

The arylation of sterically hindered amines represents one the long-standing challenges in synthetic chemistry. Herein, we report a highly efficient Ni-catalysed primary and secondary with aryl chlorides or phenol derivatives enabled by an unsymmetric N-heterocyclic carbene (NHC) ligand. protocol provides general, efficient, scalable access to various demanding anilines excellent yields under mild conditions. A wide range functional groups heterocycles are compatible (>50 examples), including those present biologically relevant molecules. Computational studies suggest that bulky flexible NHC ligand was critical balance oxidative addition reductive elimination elementary steps, thus promoting this challenging transformation.

Language: Английский

Enantioselective C–C cross-coupling of unactivated alkenes DOI
Zi-Chao Wang, Xiaohua Luo, Jiawen Zhang

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(11), P. 1087 - 1097

Published: Oct. 5, 2023

Language: Английский

Citations

25
Asymmetric Total synthesis of Asperones A and B through Organocatalyzed Quinone [5 + 2] Cycloaddition DOI

Chunlei Qu,

Lu Chen, Peng Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 13, 2025

The first asymmetric total synthesis of the anti-inflammatory polyketides asperones A (1) and B (2) has been accomplished. Key synthetic steps include a Diels-Alder retro-Diels-Alder cascade to construct poly substituted phenol, an Al-Salen-catalyzed cyanosilylation form tertiary alcohol gregatin A, organocatalyzed intermolecular [5 + 2] cycloaddition p-quinone with electron-deficient alkenes build crucial [3.2.1] octane core (2).

Language: Английский

Citations

2
Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence DOI Creative Commons
Tristan von Münchow, Neeraj Kumar Pandit, Suman Dana

et al.

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Language: Английский

Citations

1
Copper-catalysed dynamic kinetic asymmetric C−O cross-coupling to access chiral aryl oxime ethers and diaryl ethers DOI Creative Commons

Meiru Zhang,

Haoran Wang,

Hui-Mei Shan

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 13, 2025

Dynamic kinetic resolution (DKR) has emerged as an elegant and powerful tool for enantioselective synthesis, enabling the transformation of racemic compounds into enantiomerically enriched products with theoretically quantitative yields. Despite its widespread success, dynamic asymmetric C−O cross-coupling presented significant challenges remains unexplored. In this study, we report a oximes phenols via copper/BOX-catalysed O-arylation diaryliodonium salts. This method efficiently produces wide range inherently chiral oxime ethers, well axially styrenes, high yields excellent regio- enantioselectivities. Through controlled experiments Density Functional Theory (DFT) studies, have elucidated process gained insights origins enantioselectivity. The Here, authors

Language: Английский

Citations

1
Asymmetric Carbohydroxylation of Alkenes Using Photoenzymatic Catalysis DOI

Yao Ouyang,

Joshua Turek-Herman,

Tianzhang Qiao

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17018 - 17022

Published: July 27, 2023

Alkene difunctionalizations enable the synthesis of structurally elaborated products from simple and ubiquitous starting materials in a single chemical step. Carbohydroxylations olefins represent family reactivity that furnish complex alcohols. While examples this type three-component coupling have been reported, catalytic asymmetric remain elusive. Here, we report an enzyme-catalyzed carbohydroxylation alkenes catalyzed by flavin-dependent "ene"-reductases to produce enantioenriched tertiary Seven rounds protein engineering reshape enzyme's active site increase activity enantioselectivity. Mechanistic studies suggest C–O bond formation occurs via 5-endo-trig cyclization with pendant ketone afford α-oxy radical which is oxidized hydrolyzed form product. This work demonstrates photoenzymatic reactions involving can terminate radicals mechanisms other than hydrogen atom transfer, expanding their utility synthesis.

Language: Английский

Citations

19
Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts DOI

Bo‐Chao Ye,

Wenhao Li, Xia Zhang

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Language: Английский

Citations

8
Dynamic kinetic asymmetric allylation, propargylation and crotylation of ketones using copper catalysis DOI
Bo Sun,

Lin‐Xin Ruan,

Ruyuan Zhao

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(9), P. 1091 - 1103

Published: June 25, 2024

Language: Английский

Citations

6
Nickel-catalyzed acylzincation of allenes with organozincs and CO DOI Creative Commons
Xianqing Wu, Chenglong Wang, Ning Liu

et al.

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

Published: Oct. 31, 2023

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence allene and alkylzinc reagent 1 atm under mild conditions. This protocol is featured by broad functional group tolerance high selectivity, providing a rapid convenient synthetic method for diverse fully substituted benzotropone derivatives. Mechanistic studies reveal that installation cyano tethered to moiety enables regio- stereoselectivity this acylzincation allene, allowing selective formation three consecutive C-C bonds efficient manner.

Language: Английский

Citations

13
Bifunctional NHC-Promoted C2-Alkylation of Pyridine via Ni–Al Bimetallic-Catalyzed Hydroarylation of Unactivated Alkenes DOI
Binyang Jiang, Jiaming Liu, Shi‐Liang Shi

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(9), P. 6068 - 6075

Published: April 18, 2023

Achieving site-selective alkylation with pyridine under transition metal catalysis has remained a long-standing challenge, especially when using unactivated alkene as an alkylating reagent. We herein describe C2-alkylation of Ni–Al bimetallic and directing bifunctional N-heterocyclic carbene (NHC) ligand through hydroarylation alkenes. A broad range C2-alkylated pyridines various functionalities could be prepared in high efficiency (up to 99% yield) C2-selectivity, the scope heterocycles is not limited but can expanded other azines like pyrazines pyrimidines. Mechanistic studies suggest that NHC–Ni–Al–pyridine complex responsible for site selectivity control reductive elimination might rate-determining step.

Language: Английский

Citations

12
Synthesis of Enantioenriched 1,2‐cis Disubstituted Cycloalkanes by Convergent NiH Catalysis DOI
Changpeng Chen,

Wenqing Guo,

Deyong Qiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 20, 2023

Enantioenriched multi-substituted cycloalkanes constitute an essential class of compounds in pharmaceuticals, natural products and agrochemicals. Here we report NiH-catalyzed asymmetric migratory hydroalkylation process for the efficient selective construction such compounds. Through a dynamic kinetic transformation (DYKAT), easily accessible racemic isomeric mixtures cycloalkenes could be directly utilized as starting materials, convergently producing thermo-dynamically disfavored chiral 1,2-cis disubstituted bearing vicinal stereocenters with high levels regio-, diastereo- enantioselectivity. In addition, prochiral cyclic alkenes can also employed, deliver through desymmetrization process.

Language: Английский

Citations

12