Review
Chemistry, Organic
Gautam Kumar, Sourav Roy, Indranil Chatterjee
Summary: Tris(pentafluorophenyl)borane (BCF) has gained significant attention in the synthetic chemistry community as a potential Lewis acid catalyst due to its thermal stability and commercial availability. Recent research has focused on exploring BCF's role in metal-free catalysis, with many new catalytic reactivities under investigation. The review mainly categorizes different types of organic transformations mediated through BCF catalysis for the formation of C-C and C-heteroatom bonds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Slawomir Rubinsztajn, Julian Chojnowski, Urszula Mizerska
Summary: Tris(pentafluorophenyl)borane (TPFPB) is a unique Lewis acid that enables the condensation between hydrosilanes (Si-H) and alkoxysilanes (Si-OR) to form siloxane bonds (Si-OSi) in the presence of TPFPB, resulting in the release of hydrocarbon (R-H) as a byproduct, known as the Piers-Rubinsztajn reaction. TPFPB also catalyzes reactions involving hydrosilanes with silanols (Si-OH), alcohols (R-OH), ethers (R-OR') or water to form siloxane bonds, alkoxysilane (Si-OR or Si-OR') or silanol (Si-OH), respectively. These Piers-Rubinsztajn reactions provide new synthetic tools for the controlled synthesis of siloxane materials under mild conditions with high yields. This review summarizes 20 years of research efforts in this field, highlights new synthetic methodologies for well-defined siloxane oligomers, polymers, and copolymers, and discusses the potential applications of these new materials. Furthermore, the mechanistic aspects of recently discovered reactions involving hydride transfer from silicon to silicon are also discussed in detail.
Article
Nanoscience & Nanotechnology
Jinbiao Jia, Jia Dong, Beibei Shi, Jihuai Wu, Yangqing Wu, Bingqiang Cao
Summary: Passivating defects to suppress recombination is an effective strategy to improve the performance of third-generation perovskite-based solar cells. The incorporation of tris(pentafluorophenyl)borane in SnO2-based planar perovskite solar cells effectively passivates Pb-0 defects, decreases grain boundaries quantity, enhances carrier transportation capability, and leads to a higher efficiency of 21.42%. Furthermore, the stability tests demonstrate that incorporating tris(pentafluorophenyl)borane in perovskite solar cells contributes to the device's stability.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Organic
Anand Gaurav, Zanjila Azeem, Pintu Kumar Mandal
Summary: This study presents an efficient and highly stereoselective alpha-C-glycosylation strategy using a catalytic amount of BCF under mild reaction conditions, which provides 2,3-unsaturated C-glycosides with broad functional group tolerance.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Kensuke Kiyokawa, Ikumi Noguchi, Takaya Nagata, Satoshi Minakata
Summary: In this study, we present a bromocyanation reaction of styrene derivatives using cyanogen bromide in the presence of tris(pentafluorophenyl)borane as a Lewis acid catalyst. The reaction proceeds through a stereospecific syn-addition and provides a straightforward approach to beta-bromonitriles.
Article
Chemistry, Organic
Kensuke Kiyokawa, Ikumi Noguchi, Takaya Nagata, Satoshi Minakata
Summary: In this study, we demonstrate the bromocyanation of styrene derivatives with cyanogen bromide using tris(pentafluorophenyl)borane as a Lewis acid catalyst. This protocol enables a stereospecific syn-addition and provides an accessible route to beta-bromonitriles.
Article
Chemistry, Multidisciplinary
Xiuling Wen, Peiquan Lu, Yong Shen, Haojie Peng, Zhuofeng Ke, Cunyuan Zhao
Summary: This study used density functional theory (DFT) calculations to elucidate the mechanism and origin of the diastereoselective cyclopropanation reaction of aryldiazodiacetate and styrene derivatives catalyzed by B(C6F5)(3). The most probable reaction mechanism was proposed, and the origin of diastereoselectivity was explained based on favorable interactions. The calculated results not only provide a detailed explanation of the mechanism but also have guiding significance for other catalytic cyclopropanation reactions.
Article
Chemistry, Physical
Hideyuki Ishihara, Jianhao Huang, Takuya Mochizuki, Manabu Hatano, Kazuaki Ishihara
Summary: A highly enantio- and diastereoselective carbonyl-ene cyclization was developed using chiral Lewis acid-assisted chiral Bronsted acid (LBA) catalysts, demonstrating high selectivity in both standard and tandem reactions. Mechanistic examinations propose a stepwise reaction pathway involving tertiary carbocation intermediates.
Article
Green & Sustainable Science & Technology
Gengshu You, Le Liu, Jin Wang, Min Zhao, Chengjie Zhao, Xu Cai, Jin Tang, Fushen Lu, Tonggang Jiu
Summary: Polythiophene-acid-based conjugated polyelectrolytes have shown promising potential as hole-transport materials for inverted planar perovskite devices. A simple and effective strategy involving tris(pentafluorophenyl)borane as a Lewis acid has been developed to regulate the aggregation of the polyelectrolytes, leading to improved efficiency of perovskite solar cells.
ADVANCED SUSTAINABLE SYSTEMS
(2021)
Article
Chemistry, Multidisciplinary
Ayan Dasgupta, Rasool Babaahmadi, Sanjukta Pahar, Katarina Stefkova, Lukas Gierlichs, Brian F. Yates, Alireza Ariafard, Rebecca L. Melen
Summary: The study focuses on metal-free organic synthesis using triarylboranes as catalysts for the selective synthesis of N-substituted pyrazoles through the generation of carbenium species. DFT studies reveal that the in situ generation of a carbenium species serves as an autocatalyst to prompt the regiospecific formation of N-substituted pyrazoles in good to excellent yields (up to 81 %).
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yuushou Nakayama, Kentaro Yamaguchi, Ryo Tanaka, Takeshi Shiono
Summary: This study investigates the selective alcoholysis of lactide catalyzed by Lewis pairs, B(C6F5)(3)-phosphines. Among the phosphines examined, tricyclohexylphosphine (Cy3P) exhibited the highest activity and selectivity in this system.
MOLECULAR CATALYSIS
(2022)
Article
Electrochemistry
Parth Raval, Margot Dhennin, Herve Vezin, Tomasz Pawlak, Pascal Roussel, Thuc-Quyen Nguyen, G. N. Manjunatha Reddy
Summary: This study investigates the p-type doping of the hole-transporting material spiromadad in perovskite solar cells. The results provide insights into the doping process and distribution in the blended material, which is crucial for improving the stability and efficiency of hybrid perovskite photovoltaics.
ELECTROCHIMICA ACTA
(2022)
Article
Chemistry, Organic
Atul Dubey, Ashwani Tiwari, Pintu Kumar Mandal
Summary: An efficient and highly regioselective method has been developed for the synthesis of 3-indolyl-C-glycosides through coupling of glycosyl trichloroacetimidates with a wide range of substituted indoles in the presence of catalytic amounts of B(C6F5)(3) within a few minutes, providing exclusively beta-stereoselective products in 64-87% yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Shuai Liang, Michael Yin Wong, Alyssa Schneider, Mengchen Liao, Gertrud Kraeuter, Maxim N. Tchoul, Yang Chen, Michael A. Brook
Summary: The study demonstrates the preparation of highly branched tri- and tetrasilphenylene monomers from commercial alkoxysilanes and p-HSiMe2C6H4SiMe2H through the Piers-Rubinsztajn reaction, followed by curing through oxidative coupling of terminal SiH groups. The resulting silicone elastomers exhibit very good thermal stability and transparency at high temperatures.
Article
Chemistry, Multidisciplinary
Teruhiko Saito, Megan R. Hill, Shao-Xiong Lennon Luo, Hong-Zhou Ye, Troy Van Voorhis, Jeremiah A. Johnson
Summary: A catalytic method for converting common unsaturated polymers into poly(acetylene)-based multiblock copolymers suitable for electronics applications is presented. This method can also be applied to the conversion of polyethylene into PA-containing multiblock materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
J. Chojnowski, S. Slomkowski, W. Fortuniak, U. Mizerska, P. Pospiech
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2020)
Article
Chemistry, Applied
Slawomir Rubinsztajn, Julian Chojnowski, Marek Cypryk, Urszula Mizerska, Pawel Uznanski, Agnieszka Walkiewicz-Pietrzykowska
APPLIED ORGANOMETALLIC CHEMISTRY
(2020)
Article
Polymer Science
W. Fortuniak, J. Chojnowski, U. Mizerska, P. Pospiech, J. Zakrzewska, S. Slomkowski
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS
(2020)
Article
Polymer Science
Slawomir Rubinsztajn, Julian Chojnowski, Urszula Mizerska, Malgorzata Basko, Pawel Uznanski, Agnieszka Walkiewicz-Pietrzykowska, Marek Cypryk
Summary: The reaction between poly(hydromethylsiloxane-co-methylphenylsiloxane) and zirconium (IV) n-propoxide in dry toluene results in the formation of a siloxane-zirconium composite. The post-reaction solution containing heterosiloxane oligomers is stable under anhydrous conditions, but exposure to moisture leads to cross-linking and the formation of thin films with excellent light transparency and increased refractive index. The coatings are characterized using ellipsometry, UV-Vis, IR, and Si-29 MAS NMR spectroscopies.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Urszula Mizerska, Witold Fortuniak, Slawomir Rubinsztajn, Julian Chojnowski
Summary: The study compared the chemical and morphological structure of polyhydromethylsiloxane microspheres obtained with different content of cross-linker. It was found that increasing the cross-linking agent content leads to significant changes in the polymer side chains and cross-links between macromolecules, affecting the surface properties of the microspheres. The research demonstrated a simple method to control the hydrophilic-hydrophobic properties of siloxane microspheres.
POLYMERS FOR ADVANCED TECHNOLOGIES
(2021)
Article
Polymer Science
Urszula Mizerska, Witold Fortuniak, Tomasz Makowski, Mariia Svyntkivska, Ewa Piorkowska, Dorota Kowalczyk, Stefan Brzezinski, Dorota Kregiel
Summary: Cotton fabric was modified with organosilicon coating containing graphene oxide and thermally reduced to reduced graphene oxide, imparting electrical conductivity, hydrophobicity, and antibacterial activity against Escherichia coli and Staphylococcus aureus.
POLYMERS FOR ADVANCED TECHNOLOGIES
(2021)
Article
Chemistry, Physical
Urszula Mizerska, Witold Fortuniak, Julian Chojnowski, Slawomir Rubinsztajn, Joanna Zakrzewska, Irena Bak-Sypien, Anna Nyczyk-Malinowska
Summary: A simple and inexpensive method for the preparation of porous SiC microspheres is presented, and the content of free carbon in SiC particles can be controlled by using different proportions of DVB. The thermal reduction processes during ceramization create a porous structure of the microspheres.
Article
Chemistry, Physical
Urszula Mizerska, Slawomir Rubinsztajn, Julian Chojnowski, Marek Cypryk, Pawel Uznanski, Agnieszka Walkiewicz-Pietrzykowska, Witold Fortuniak
Summary: The branching and cross-linking of siloxane polymers play vital roles in silicone technology. A new self-restructuring process has been developed, which transforms linear polyhydromethylsiloxane (PHMS) into highly branched siloxane polymer or cross-linked siloxane network through hydride ion transfer between silicon atoms catalyzed by tris(pentafluoromethyl)borane. Unlike existing reactions, this process operates at room temperature without the need for a low-molecular-weight cross-linker, water, silanol groups, or metal catalysts. The study of this process was conducted in toluene solution, tracking its progress through various techniques. A proposed mechanism based on quantum calculations supports this new self-restructuring process, and it has been demonstrated that a linear PHMS can serve as a precursor for pure methylsiloxane film.
Review
Biochemistry & Molecular Biology
Slawomir Rubinsztajn, Julian Chojnowski, Urszula Mizerska
Summary: Tris(pentafluorophenyl)borane (TPFPB) is a unique Lewis acid that enables the condensation between hydrosilanes (Si-H) and alkoxysilanes (Si-OR) to form siloxane bonds (Si-OSi) in the presence of TPFPB, resulting in the release of hydrocarbon (R-H) as a byproduct, known as the Piers-Rubinsztajn reaction. TPFPB also catalyzes reactions involving hydrosilanes with silanols (Si-OH), alcohols (R-OH), ethers (R-OR') or water to form siloxane bonds, alkoxysilane (Si-OR or Si-OR') or silanol (Si-OH), respectively. These Piers-Rubinsztajn reactions provide new synthetic tools for the controlled synthesis of siloxane materials under mild conditions with high yields. This review summarizes 20 years of research efforts in this field, highlights new synthetic methodologies for well-defined siloxane oligomers, polymers, and copolymers, and discusses the potential applications of these new materials. Furthermore, the mechanistic aspects of recently discovered reactions involving hydride transfer from silicon to silicon are also discussed in detail.
Article
Chemistry, Inorganic & Nuclear
Slawomir Rubinsztajn, Urszula Mizerska, Joanna Zakrzewska, Pawel Uznanski, Marek Cypryk, Witold Fortuniak
DALTON TRANSACTIONS
(2020)
