Synthesis of Thiophene‐Based π‐Conjugated Oligomers via Ligand‐Enabled Pd‐Catalyzed Suzuki–Miyaura Coupling of Haloterthienyls

Guo, Jin; Wu, Yong; Kwong, Fuk Yee; Zhang, Heng; Lei, Aiwen

doi:10.1002/asia.201800395

Cited by 3 publications

(2 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Inspired by the excellent regioselectivity and high efficiency of the Pd-NHC-catalyzed cross-coupling reaction in this study, we further focused on the synthesis of poly(3-hexylthiophenes) (P3HT), which exhibits a unique combination of high environmental/thermal stability, electrical conductivity, and processability for its application in organic photovoltaic cells (OPVs), light-emitting diodes (OLEDs), and field-effect transistors (OFETs). , As shown in Scheme , the polycondensation of 2-bromo-3-hexylthiophene was carried out at a temperature of 100 °C, leading to the formation of P3HT with high molecular weight of 15.0 KDa, while the HT (head-to-tail regioselectivity) is as high as 93%. On the contrary, merely branched P3HT with low molecular weight was obtained in the ligand-free catalytic protocols, which reported was by Luscombe et al recently .…”

Section: Resultsmentioning

confidence: 99%

Bis(imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Complexes with Ancillary Ligands: Readily Activated Precatalysts for Direct C–H Arylation of Thiophenes

Zheng

Liu

et al. 2022

Organometallics

View full text Add to dashboard Cite

We report herein a highly efficient direct C−H arylation of thiophenes with (hetero)aryl bromides by bulky bis(imino)acenaphthene (BIAN)supported N-heterocyclic carbene palladium complexes. The relationship between the structure of palladium complexes with ancillary ligands and catalytic properties was discussed. Upon a low palladium loading of 0.01−0.05 mol %, the bulky palladium complex was successfully used to catalyze the cross-coupling of a variety of thiophens with (hetero)aryl bromides under aerobic conditions. Furthermore, it provides a practical and straightforward access to poly(3-hexylthiophenes) with high molecular weight and high HT value under aerobic reaction conditions. To access the mechanistic of the transformation, experiment investigation and DFT calculations on the direct arylation were performed, which supported the involvement of a Pd (0) /Pd (II) CMD process.

show abstract

Section: Resultsmentioning

confidence: 99%

Bis(imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Complexes with Ancillary Ligands: Readily Activated Precatalysts for Direct C–H Arylation of Thiophenes

Zheng

Liu

et al. 2022

Organometallics

View full text Add to dashboard Cite

show abstract

“…Transition-metal-catalyzed cross-coupling reaction has become one of the most powerful transformations in organic synthesis for the carbon-carbon bond formation. For example, named reactions including Suzuki-Miyaura, [1] Sonogashira, [2] Heck, [3] Hiyama [4] and Stille [5] reactions have revolutionized avenues to access organic molecules. These homogeneous catalytic processes have been extensively used in both academic and industrial fields, [6] providing important compounds including pharmaceuticals, [7] agrochemicals, [8] natural products, [9] polymer materials [10] and so on.…”

Section: Introductionmentioning

confidence: 99%

Shuttling Catalyst: Facilitating C−C Bond Formation via Cross‐Couplings with a Thermoresponsive Polymeric Ligand

Wang

Zhang

Zhong

et al. 2019

Israel Journal of Chemistry

View full text Add to dashboard Cite

A poly(ethylene glycol) (PEG) linked ortho-MeOphenyldicyclohexylphosphine (MeO-WePhos) ligand has been synthesized to promote Pd-catalyzed carbon-carbon bond formation by cross-couplings including Sonogashira, Heck, Hiyama and Stille reactions, providing corresponding (hetero)aryl substituted alkynes, alkenes and bi(hetero)aryls in good to excellent isolated yields with low Pd loadings. Facilitated by the lower critical solution temperature behaviour of the polymeric monophosphine ligand, the metalcomplex could rapidly shuttle between organic and water phases as regulated by temperature, enabling highly efficient catalyst recycling via a simple phase separation. The chemical structure of ligand was determined by matrixassisted laser desorption/ionization-time of flight mass spectrometry, nuclear magnetic resonance spectrometry and size-exclusion chromatography measurements. Notably, as demonstrated by the inductively coupled plasma-atomic emission spectrometry measurement, 98% Pd was kept in the water phase after 6 cycles of catalyst recycling experiments. Given the profound impact of transition-metalcatalyzed covalent bond formation and the increasing demand of sustainable chemistry, this work provides an alternative method to conduct cross-couplings with a polymeric shuttling catalyst. Scheme 5. Hiyama and Stille reaction with MeO-WePhos 5000 4 a. Conditions: 23 (0.5 mmol), 24 (0.6 mmol), K 2 CO 3 (1.0 mmol), water (0.8 mL), toluene (0.2 mL), 90°C, 6 h. Isolated yields are based on aryl bromides 23.

show abstract

A Highly Efficient Monophosphine Ligand for Parts per Million Levels Pd‐Catalyzed Suzuki–Miyaura Coupling of (Hetero)Aryl Chlorides

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis of Thiophene‐Based π‐Conjugated Oligomers via Ligand‐Enabled Pd‐Catalyzed Suzuki–Miyaura Coupling of Haloterthienyls

Cited by 3 publications

References 26 publications

Bis(imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Complexes with Ancillary Ligands: Readily Activated Precatalysts for Direct C–H Arylation of Thiophenes

Bis(imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Complexes with Ancillary Ligands: Readily Activated Precatalysts for Direct C–H Arylation of Thiophenes

Shuttling Catalyst: Facilitating C−C Bond Formation via Cross‐Couplings with a Thermoresponsive Polymeric Ligand

A Highly Efficient Monophosphine Ligand for Parts per Million Levels Pd‐Catalyzed Suzuki–Miyaura Coupling of (Hetero)Aryl Chlorides

Contact Info

Product

Resources

About