Functionalized Phosphorus‐Doped Porous Organic Polymers (FPPOPs)‐Promoted Pd‐Catalyzed Arylation of Hydrosilanes DOI
Yilin Chen,

Sisi Tian,

Yan Wang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(47)

Published: Aug. 20, 2024

Abstract The development of novel catalyst systems, especially as highly efficient heterogeneous catalysts for Si−C bond ‐forming arylation reaction hydrosilanes is desirable. Herein, we developed a simple and eco‐friendly methodology construction functionalized phosphorus‐doped porous organic polymers (FPPOPs) its palladium through anchoring on FPPOPs bearing phosphine ligand, in which the fabrication was completed vinyl‐substituted triphenylphosphine (ViPPh 3 ) polyhedral oligomeric silsequioxane (ViPOSS) well functional olefins via radical co‐polymerization. All these could act ligand Pd‐catalyzed have been characterized by SEM, FTIR, X‐RAD. Moreover, POSS‐based (POSS‐PPOPs) proved to be high efficiency system with aryl iodides good yields excellent chemoselectivity low amount under mild conditions. mechanistic studies supported effect group catalytic activity Pd/FPPOPs catalyst, revealed that weak coordination non‐covalent interaction between substrate played important role enhancement chemoselectivity.

Language: Английский

Nickel-catalyzed cross-electrophile couplings of aryl fluorosulfates with vinyl chlorosilanes DOI

Jin-He Na,

Hong-Jian Du,

Jia-Wen Jing

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 437, P. 115636 - 115636

Published: July 6, 2024

Language: Английский

Citations

10
Synthesis of Alkynylsilanes: A Review of the State of the Art DOI
Krzysztof Kuciński

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(11), P. 2382 - 2431

Published: April 12, 2024

Abstract This contribution offers a comprehensive overview of methods for forging sp C−Si bonds. Over time, alkynylsilanes (silylacetylenes), once considered mere byproducts hydrosilylation processes, have become essential building blocks in organic synthesis. literature review traces the evolution their synthesis, from traditional methodologies relying on organolithium and organomagnesium compounds to more advanced cross‐coupling reactions involving hydro‐ carbosilanes. Focused primarily past 25 years (2000–2024), it also extensively references significant historical breakthroughs. By analyzing synthetic methodologies, not only survey current state knowledge but identifies areas improvement. Furthermore, emphasize importance 1‐alkynylsilanes (1‐silyl‐1‐alkynes), selected applications these are highlighted, confirming potential

Language: Английский

Citations

6
Enantioselective and Regiodivergent Synthesis of Propargyl‐ and Allenylsilanes through Catalytic Propargylic C−H Deprotonation DOI Creative Commons
Jin Zhu,

Hengye Xiang,

Hai Won Chang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 13, 2024

Abstract We report a highly enantioselective intermolecular C−H bond silylation catalyzed by phosphoramidite‐ligated iridium catalyst. Under reagent‐controlled protocols, propargylsilanes resulting from C(sp 3 )−H functionalization, as well the regioisomeric and synthetically versatile allenylsilanes, could be obtained with excellent levels of enantioselectivity good to control propargyl/allenyl selectivity. In case unsymmetrical dialkyl acetylenes, selectivity for functionalization at less‐hindered site was also observed. A variety electrophilic silyl sources (R SiOTf R SiNTf 2 ), either commercial or in situ ‐ generated, were used reagents, broad range simple functionalized alkynes, including aryl alkyl 1,3‐enynes, drug derivatives successfully employed substrates. Detailed mechanistic experiments DFT calculations suggest that an η ‐propargyl/allenyl Ir intermediate is generated upon π‐complexation‐assisted deprotonation undergoes outer‐sphere attack silylating reagent give propargylic silanes, latter step identified enantiodetermining step.

Language: Английский

Citations

5
Synthesis of 1‐Aryl‐β‐Carbolines via a Pd‐Catalyzed Oxidative Pictet‐Spengler Reaction/Aromatization Cascade Using Benzylic Alcohols in Water DOI Open Access
Masakazu Kobayashi, Hidemasa Hikawa,

Tomokatsu Enda

et al.

European Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Abstract We report a Pd‐catalyzed oxidative Pictet‐Spengler reaction/aromatization cascade utilizing readily available benzylic alcohols for the construction of 1‐aryl‐ β ‐carbolines in water. Conceptually, this novel one‐pot, three‐step approach involves an initial Pd(0)/sodium diphenylphosphinobenzene‐3‐sulfonate (TPPMS)‐catalyzed dehydrogenation alcohols, followed by cyclization situ generated aldehydes with tryptamines, and concludes DBU/air‐promoted aromatization, allowing rapid access to desired ‐carbolines. The π ‐benzylPd (II) catalytic system from Pd(0)/TPPMS was found be highly effective alcohol

Language: Английский

Citations

0
One-Pot Sequential Alcohol Activation and Nickel-Catalyzed Cross-Electrophile Coupling with Chlorosilanes DOI Creative Commons

Xiaojie Liu,

Biping Xu, Martin Oestreich

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 31, 2025

A formal deoxygenative silylation of primary alcohols is reported. The one-pot procedure consists an in situ bromination the alcohol and a subsequent nickel-catalyzed cross-electrophile coupling formed alkyl bromide various vinyl-substituted chlorosilanes. key to success compatibility nickel catalysis as well chlorosilane electrophile with byproducts preceding step, especially triphenylphosphine oxide likely acting weak ligand for excess catalyst used.

Language: Английский

Citations

0
Enantioselective and Regiodivergent Synthesis of Propargyl‐ and Allenylsilanes through Catalytic Propargylic C−H Deprotonation DOI
Jin Zhu,

Hengye Xiang,

Hai Won Chang

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(16)

Published: Feb. 13, 2024

Abstract We report a highly enantioselective intermolecular C−H bond silylation catalyzed by phosphoramidite‐ligated iridium catalyst. Under reagent‐controlled protocols, propargylsilanes resulting from C(sp 3 )−H functionalization, as well the regioisomeric and synthetically versatile allenylsilanes, could be obtained with excellent levels of enantioselectivity good to control propargyl/allenyl selectivity. In case unsymmetrical dialkyl acetylenes, selectivity for functionalization at less‐hindered site was also observed. A variety electrophilic silyl sources (R SiOTf R SiNTf 2 ), either commercial or in situ ‐ generated, were used reagents, broad range simple functionalized alkynes, including aryl alkyl 1,3‐enynes, drug derivatives successfully employed substrates. Detailed mechanistic experiments DFT calculations suggest that an η ‐propargyl/allenyl Ir intermediate is generated upon π‐complexation‐assisted deprotonation undergoes outer‐sphere attack silylating reagent give propargylic silanes, latter step identified enantiodetermining step.

Language: Английский

Citations

0
Functionalized Phosphorus‐Doped Porous Organic Polymers (FPPOPs)‐Promoted Pd‐Catalyzed Arylation of Hydrosilanes DOI
Yilin Chen,

Sisi Tian,

Yan Wang

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(47)

Published: Aug. 20, 2024

Abstract The development of novel catalyst systems, especially as highly efficient heterogeneous catalysts for Si−C bond ‐forming arylation reaction hydrosilanes is desirable. Herein, we developed a simple and eco‐friendly methodology construction functionalized phosphorus‐doped porous organic polymers (FPPOPs) its palladium through anchoring on FPPOPs bearing phosphine ligand, in which the fabrication was completed vinyl‐substituted triphenylphosphine (ViPPh 3 ) polyhedral oligomeric silsequioxane (ViPOSS) well functional olefins via radical co‐polymerization. All these could act ligand Pd‐catalyzed have been characterized by SEM, FTIR, X‐RAD. Moreover, POSS‐based (POSS‐PPOPs) proved to be high efficiency system with aryl iodides good yields excellent chemoselectivity low amount under mild conditions. mechanistic studies supported effect group catalytic activity Pd/FPPOPs catalyst, revealed that weak coordination non‐covalent interaction between substrate played important role enhancement chemoselectivity.

Language: Английский

Citations

0