Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Triphenylborane in Metal-Free Catalysis

Journal Article · · Molecules

The development and application of new organoboron reagents as Lewis acids in synthesis and metal-free catalysis have dramatically expanded over the past 20 years. In this context, we will show the recent uses of the simple and relatively weak Lewis acid BPh3—discovered 100 years ago—as a metal-free catalyst for various organic transformations. The first part will highlight catalytic applications in polymer synthesis such as the copolymerization of epoxides with CO2, isocyanate, and organic anhydrides to various polycarbonate copolymers and controlled diblock copolymers as well as alternating polyurethanes. This is followed by a discussion of BPh3 as a Lewis acid component in the frustrated Lewis pair (FLP) mediated cleavage of hydrogen and hydrogenation catalysis. In addition, BPh3-catalyzed reductive N-methylations and C-methylations with CO2 and silane to value-added organic products will be covered as well along with BPh3-catalyzed cycloadditions and insertion reactions. Collectively, this mini-review showcases the underexplored potential of commercially available BPh3 in metal-free catalysis.

Research Organization:
Texas Tech Univ., Lubbock, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
SC0019094;
OSTI ID:
2420944
Journal Information:
Molecules, Journal Name: Molecules Journal Issue: 3 Vol. 28; ISSN MOLEFW; ISSN 1420-3049
Publisher:
MDPI
Country of Publication:
United States
Language:
English

References (78)

Catalysis without Precious Metals book August 2010
From Blue to Red: Syntheses, Structures, Electronic and Electroluminescent Properties of Tunable Luminescent N,N Chelate Boron Complexes journal January 2005
Rational Color Tuning and Luminescent Properties of Functionalized Boron-Containing 2-Pyridyl Pyrrolide Complexes journal April 2005
Expanding the Scope of Metal-Free Catalytic Hydrogenation through Frustrated Lewis Pair Design journal June 2010
Reaction of Frustrated Lewis Pairs with Conjugated Ynones-Selective Hydrogenation of the Carbon-Carbon Triple Bond journal June 2011
Selective Reduction of Amides to Amines by Boronic Acid Catalyzed Hydrosilylation journal September 2013
Metal-Free Hydrogenation of Unsaturated Hydrocarbons Employing Molecular Hydrogen journal February 2014
Developing Conjugated Polymers with High Electron Affinity by Replacing a CC Unit with a B N Unit journal February 2015
Chemoselective Reduction of Tertiary Amides to Amines Catalyzed by Triphenylborane journal October 2016
Perfectly Alternating and Regioselective Copolymerization of Carbonyl Sulfide and Epoxides by Metal-Free Lewis Pairs journal April 2017
Polyurethanes from Direct Organocatalytic Copolymerization of p ‐Tosyl Isocyanate with Epoxides journal November 2020
Metal‐Free Catalytic Hydrogenolysis of Silyl Triflates and Halides into Hydrosilanes** journal April 2022
Dihydrogen Splitting Using Dialkylsilylene-Based Frustrated Lewis Pairs journal March 2017
Darstellung von organischen Bor‐Verbindungen mit Hilfe von Borfluorid, II.: Bortriphenyl und Phenyl‐borsäure journal May 1922
Eine Reihe auffallend beständiger Nebenvalenz‐Verbindungen des Bortriphenyls, ein Beitrag zum Valenzproblem des Bors journal May 1924
Benzo[c,d]indole-Containing Aza-BODIPY Dyes: Asymmetrization-Induced Solid-State Emission and Aggregation-Induced Emission Enhancement as New Properties of a Well-Known Chromophore journal July 2015
Selective Metal-Free Hydrosilylation of CO 2 Catalyzed by Triphenylborane in Highly Polar, Aprotic Solvents journal April 2016
Expanding Water/Base Tolerant Frustrated Lewis Pair Chemistry to Alkylamines Enables Broad Scope Reductive Aminations journal January 2017
“Inverse” Frustrated Lewis Pairs: An Inverse FLP Approach to the Catalytic Metal Free Hydrogenation of Ketones journal October 2018
Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale journal January 2021
Mechanism of BPh3‐Catalyzed N‐Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane journal September 2022
B(C 6 F 5 ) 3 ‐Catalyzed sp 3 C—Si Bond Forming Consecutive Reactions journal September 2019
New Synthetic Strategies for Structured Silicones Using B(C6F5)3 book January 2010
Die kristall- und molekülstruktur des triphenylborans journal June 1974
Hydrosilane synthesis via catalytic hydrogenolysis of halosilanes using a metal-ligand bifunctional iridium catalyst journal August 2018
Tris(pentafluorophenyl)borane and Beyond: Modern Advances in Borylation Chemistry journal February 2017
Hydrosilane Synthesis by Catalytic Hydrogenolysis of Chlorosilanes and Silyl Triflates journal October 2018
The Role of (tBuPOCOP)Ir(I) and Iridium(III) Pincer Complexes in the Catalytic Hydrogenolysis of Silyl Triflates into Hydrosilanes journal November 2021
Controlling the Lewis Acidity and Polymerizing Effectively Prevent Frustrated Lewis Pairs from Deactivation in the Hydrogenation of Terminal Alkynes journal April 2021
BPh3-Catalyzed [2+3] Cycloaddition of Ph3PCCO with Aldonitrones: Access to 5-Isoxazolidinones with Exocyclic Phosphonium Ylide Moieties journal July 2019
Unlocking the Catalytic Hydrogenolysis of Chlorosilanes into Hydrosilanes with Superbases journal August 2021
Facile Protocol for Water-Tolerant “Frustrated Lewis Pair”-Catalyzed Hydrogenation journal August 2015
B(C6F5)3-Catalyzed Reductive Amination using Hydrosilanes journal February 2016
Triarylborane-Catalyzed Formation of Cyclic Organic Carbonates and Polycarbonates journal January 2019
Synthesis, Structure, and Electroluminescence of BR2q (R = Et, Ph, 2-Naphthyl and q = 8-Hydroxyquinolato) journal December 1999
Metal-Free Catalytic Hydrogenation of Polar Substrates by Frustrated Lewis Pairs journal December 2011
Facile Heterolytic Cleavage of Dihydrogen by Phosphines and Boranes journal February 2007
Homogeneous CO Hydrogenation: Dihydrogen Activation Involves a Frustrated Lewis Pair Instead of a Platinum Complex journal March 2010
Tandem Frustrated Lewis Pair/Tris(pentafluorophenyl)borane-Catalyzed Deoxygenative Hydrosilylation of Carbon Dioxide journal August 2010
A Zwitterionic Carbanion Frustrated by Boranes – Dihydrogen Cleavage with Weak Lewis Acids via an “Inverse” Frustrated Lewis Pair Approach journal October 2013
Rationalizing the Reactivity of Frustrated Lewis Pairs: Thermodynamics of H 2 Activation and the Role of Acid−Base Properties journal August 2009
B/N-Doped p-Arylenevinylene Chromophores: Synthesis, Properties, and Microcrystal Electron Crystallographic Study journal October 2020
Dimerization and Cycloaddition Reactions of Transient Tri-tert-butylphosphacyclobutadiene Generated by Lewis Acid Induced Isomerization of Tri-tert-butylphosphatetrahedrane journal August 2021
“Inverse” Frustrated Lewis Pairs – Activation of Dihydrogen with Organosuperbases and Moderate to Weak Lewis Acids journal March 2016
Metal-Free Alternating Copolymerization of CO2 with Epoxides: Fulfilling “Green” Synthesis and Activity journal August 2016
BORAZANs:  Tunable Fluorophores Based on 2-(Pyrazolyl)aniline Chelates of Diphenylboron journal June 2007
Metal-Free Reduction of Secondary and Tertiary N-Phenyl Amides by Tris(pentafluorophenyl)boron-Catalyzed Hydrosilylation journal July 2014
Application of (Triphenylphosphinemethyl- ene)boranes to Thermally Latent Catalysts for Polyaddition of Bisphenol A Diglycidyl Ether with Bisphenol A:  Model System of Epoxy−Novolac Resin journal January 2001
Substituent Effect of (Triphenylphosphinemethylene)boranes on Latent Catalytic Activity for Polyaddition of Bisphenol A Diglycidyl Ether with Bisphenol A:  Model System of Epoxy−Novolac Resin journal December 2001
Synthesis of Organoboron Quinoline-8-thiolate and Quinoline-8-selenolate Complexes and Their Incorporation into the π-Conjugated Polymer Main-Chain journal March 2009
Facile Synthesis of Highly Fluorescent Boranil Complexes journal June 2011
Synthesis and Fluorescence Properties of Novel Pyrazine–Boron Complexes Bearing a β-Iminoketone Ligand journal November 2011
Hydrogenation by Frustrated Lewis Pairs: Main Group Alternatives to Transition Metal Catalysts? journal February 2014
A frustrated-Lewis-pair approach to catalytic reduction of alkynes to cis-alkenes journal July 2013
Construction of full-color-tunable and strongly emissive materials by functionalizing a boron-chelate four-ring-fused π-conjugated core journal January 2012
Efficient metal-free hydrosilylation of tertiary, secondary and primary amides to amines journal January 2014
Aggregation-induced emission (AIE) of pyridyl-enamido-based organoboron luminophores journal January 2015
A unified survey of Si–H and H–H bond activation catalysed by electron-deficient boranes journal January 2015
A family of N-heterocyclic carbene-stabilized borenium ions for metal-free imine hydrogenation catalysis journal January 2015
DBU/benzyl bromide: an efficient catalytic system for the chemical fixation of CO2 into cyclic carbonates under metal- and solvent-free conditions journal January 2016
An efficient metal- and solvent-free organocatalytic system for chemical fixation of CO2 into cyclic carbonates under mild conditions journal January 2016
An organoboron compound with a wide absorption spectrum for solar cell applications journal January 2017
Diphosphination of CO 2 and CS 2 mediated by frustrated Lewis pairs – catalytic route to phosphanyl derivatives of formic and dithioformic acid journal January 2019
Lewis acid base chemistry of Bestmann's ylide, Ph3PCCO, and its bulkier analogue, (cyclohexyl)3PCCO journal January 2019
Functionalized polycarbonates via triphenylborane catalyzed polymerization-hydrosilylation journal January 2019
Tris(pentafluorophenyl)borane catalyzed C–C and C–heteroatom bond formation journal January 2021
Borane catalyzed polymerization and depolymerization reactions controlled by Lewis acidic strength journal January 2021
Deoxygenative CO2 conversions with triphenylborane and phenylsilane in the presence of secondary amines or nitrogen-containing aromatics journal January 2022
The ultimate Lewis acid catalyst: using tris(pentafluorophenyl) borane to create bespoke siloxane architectures journal January 2022
Tris(pentafluorophenyl)borane: a special boron Lewis acid for special reactions journal January 2005
Rapid intramolecular heterolytic dihydrogen activation by a four-membered heterocyclic phosphane–borane adduct journal January 2007
Brightly fluorescent red organic solids bearing boron-bridged π–conjugated skeletons journal January 2011
“Frustrated Lewis pair” hydrogenations journal January 2012
Pentafluorophenylboranes: from obscurity to applications journal January 1997
Reversible, Metal-Free Hydrogen Activation journal November 2006
Ir-catalyzed Hydrogenolysis Reaction of Silyl Triflates and Halides with H2 journal October 2017
Boron-Based Lewis Acid Catalysis: Challenges and Perspectives journal December 2021
Tris(pentafluorophenyl)borane-Catalyzed Reactions Using Silanes journal January 2019

Similar Records

Triphenylborane in Metal-Free Catalysis
Journal Article · 2023 · Molecules · OSTI ID:1922980

Covalency-Driven Differences in the Hydrogenation Chemistry of Lanthanide- and Actinide-Based Frustrated Lewis Pairs
Journal Article · 2024 · Journal of the American Chemical Society · OSTI ID:2459304