Hydroboration
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Asymmetric Synthesis of Secondary and Tertiary Boronic Esters Open
Non‐racemic chiral boronic esters are recognised as immensely valuable building blocks in modern organic synthesis. Their stereospecific transformation into a variety of functional groups—from amines and halides to arenes and alkynes—along…
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Tris(pentafluorophenyl)borane and Beyond: Modern Advances in Borylation Chemistry Open
As main-group chemistry, in particular boron chemistry, has expanded and developed over the past 20 years, one reagent has risen to prominence as well. Tris(pentafluorophenyl)borane, B(C6F5)3 (commonly known as BCF), has demonstrated exten…
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The transition metal-catalysed hydroboration reaction Open
This review covers the development of the transition metal-catalysed hydroboration reaction, from its beginnings in the 1980s to more recent developments including earth-abundant catalysts and an ever-expanding array of substrates.
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Magnesium-catalysed nitrile hydroboration Open
A β-diketiminaton-butylmagnesium complex is presented as a selective precatalyst for the reductive hydroboration of organic nitriles with pinacolborane (HBpin).
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Asymmetric remote C-H borylation of internal alkenes via alkene isomerization Open
Recent years have witnessed the growing interest in the remote functionalization of alkenes for it offers a strategy to activate the challenging C–H bonds distant from the initiation point via alkene isomerization/functionalization. Howeve…
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Mechanistic Studies of Copper-Catalyzed Asymmetric Hydroboration of Alkenes Open
Mechanistic studies of the copper-catalyzed asymmetric hydroboration of vinylarenes and internal alkenes are reported. Catalytic systems with both DTBM-SEGPHOS and SEGPHOS as the ligands have been investigated. With DTBM-SEGPHOS as the lig…
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Cobalt-Catalyzed 1,1-Diboration of Terminal Alkynes: Scope, Mechanism, and Synthetic Applications Open
A cobalt-catalyzed method for the 1,1-diboration of terminal alkynes with bis(pinacolato)diboron (B2Pin2) is described. The reaction proceeds efficiently at 23 °C with excellent 1,1-selectivity and broad functional group tolerance. With th…
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Aluminum Hydride Catalyzed Hydroboration of Alkynes Open
An aluminum‐catalyzed hydroboration of alkynes using either the commercially available aluminum hydride DIBAL‐H or bench‐stable Et 3 Al⋅DABCO as the catalyst and H‐Bpin as both the boron reagent and stoichiometric hydride source has been d…
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Aluminum-Catalyzed Hydroboration of Alkenes Open
The aluminum-catalyzed hydroboration of alkenes with HBpin is reported using simple commercially available aluminum hydride precatalysts [LiAlH4 or sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al)]. Good substrate scope and functional …
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s-Block Metal Catalysts for the Hydroboration of Unsaturated Bonds Open
The addition of a B-H bond to an unsaturated bond (polarized or unpolarized) is a powerful and atom-economic tool for the synthesis of organoboranes. In recent years, s-block organometallics have appeared as alternative catalysts to transi…
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Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin Open
Simple nucleophiles with structural similarities to known hydroboration catalysts can readily mediate the formation of BH3 and borohydride species from pinacolborane (HBpin). Alkyne and alkene hydroboration reactions were successfully medi…
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Site-Selective and Stereoselective <i>trans</i>-Hydroboration of 1,3-Enynes Catalyzed by 1,4-Azaborine-Based Phosphine–Pd Complex Open
A concise synthesis of monobenzofused 1,4-azaborine phosphine ligands (Senphos) is described. These Senphos ligands uniquely support Pd-catalyzed trans-selective hydroboration of terminal and internal 1,3-enynes to furnish corresponding di…
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Group 6 Transition‐Metal/Boron Frustrated Lewis Pair Templates Activate N<sub>2</sub>and Allow its Facile Borylation and Silylation Open
The reaction of trans ‐[M(N 2 ) 2 (dppe) 2 ] (M=Mo, 1 Mo , M=W, 1 W ) with B(C 6 F 5 ) 3 ( 2 ) provides the adducts [(dppe) 2 M=N=N‐B(C 6 F 5 ) 3 ] ( 3 ) which can be regarded as M/B transition‐metal frustrated Lewis pair (TMFLP) templates…
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Low-Coordinate NHC–Zinc Hydride Complexes Catalyze Alkyne C–H Borylation and Hydroboration Using Pinacolborane Open
Organozinc compounds containing sp, sp2, and sp3 C-Zn moieties undergo transmetalation with pinacolborane (HBPin) to produce Zn-H species and organoboronate esters (RBPin). This Zn-C/H-B metathesis step is key to enabling zinc-catalyzed bo…
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Enantioselective Rhodium(III)-Catalyzed Markovnikov Hydroboration of Unactivated Terminal Alkenes Open
We report the first enantioselective Rh-catalyzed Markovnikov hydroboration of unactivated terminal alkenes. Using a novel sp2-sp3 hybridized diboron reagent and water as a proton source, a broad range of alkenes undergo hydroboration to p…
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Implications of CO<sub>2</sub> Activation by Frustrated Lewis Pairs in the Catalytic Hydroboration of CO<sub>2</sub>: A View Using N/Si<sup>+</sup> Frustrated Lewis Pairs Open
A series of base-stabilized silylium species were synthesized and their reactivity toward CO2 explored, yielding the characterization of a novel N/Si+ FLP-CO2 adduct. These silicon species are active catalysts in the hydroboration of CO2 t…
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Highly selective catalytic trans-hydroboration of alkynes mediated by borenium cations and B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub> Open
Transition metal free alkyne trans-hydroboration is achieved using strong boron electrophiles in the presence of a B–H moiety.
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Hydroboration of Carbon Dioxide Using Ambiphilic Phosphine–Borane Catalysts: On the Role of the Formaldehyde Adduct Open
Ambiphilic phosphine–borane derivatives 1-B(OR)2-2-PR′2–C6H4 (R′ = Ph (1), iPr (2); (OR)2 = (OMe)2 (1a, 2a); catechol (1b, 2b) pinacol (1c, 2c), −OCH2C(CH3)2CH2O– (1d)) were tested as catalysts for the hydroboration of CO2 using HBcat or B…
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Tris(2,4,6‐trifluorophenyl)borane: An Efficient Hydroboration Catalyst Open
The metal‐free catalyst tris (2,4,6‐trifluorophenyl)borane has demonstrated its extensive applications in the 1,2‐hydroboration of numerous unsaturated reagents, namely alkynes, aldehydes and imines, consisting of a wide array of electron‐…
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Manganese‐Catalyzed Hydrofunctionalization of Alkenes Open
The manganese‐catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields ac…
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P–N Cooperative Borane Activation and Catalytic Hydroboration by a Distorted Phosphorous Triamide Platform Open
Studies of the stoichiometric and catalytic reactivity of a geometrically constrained phosphorous triamide 1 with pinacolborane (HBpin) are reported. The addition of HBpin to phosphorous triamide 1 results in cleavage of the B-H bond of pi…
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Lithium diamidodihydridoaluminates: bimetallic cooperativity in catalytic hydroboration and metallation applications Open
Cooperativity between the Li and Al centres is implicated in catalytic hydroboration reactions of aldehydes and ketones with pinacolborane via heteroleptic lithium diamidodihydridoaluminates.
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Mechanism‐Based Enantiodivergence in Manganese Reduction Catalysis: A Chiral Pincer Complex for the Highly Enantioselective Hydroboration of Ketones Open
A manganese alkyl complex containing a chiral bis(oxazolinyl‐methylidene)isoindoline pincer ligand is a precatalyst for a catalytic system of unprecedented activity and selectivity in the enantioselective hydroboration of ketones, thus pro…
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Hydrosilylation and hydroboration in a sustainable manner: from Earth-abundant catalysts to catalyst-free solutions Open
Hydroelementation enables a facile reduction or functionalization of several unsaturated systems, and thus activation of such bonds like B–H and Si–H is a powerful synthetic tool.
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Synthesis of 1,1-diboronate esters by cobalt-catalyzed sequential hydroboration of terminal alkynes Open
Co-catalyzed sequential hydroborations of alkyl and aryl alkynes with pinacolborane produce 1,1-diboronate esters with high selectivity and yields.
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Markovnikov-Selective, Activator-Free Iron-Catalyzed Vinylarene Hydroboration Open
Two series of structurally related alkoxy-tethered NHC iron(II) complexes have been developed as catalysts for the regioselective hydroboration of alkenes. Significantly, Markonikov-selective alkene hydroboration with HBpin has been contro…
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Emergence and Applications of Base Metals (Fe, Co, and Ni) in Hydroboration and Hydrosilylation Open
Base metal catalysis offers an alternative to reactions, which were once dominated by precious metals in hydrofunctionalization reactions. This review article details the development of some base metals (Fe, Co, and Ni) in the hydroboratio…
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Direct and Transfer Hydrosilylation Reactions Catalyzed by Fully or Partially Fluorinated Triarylboranes: A Systematic Study Open
The present survey serves several purposes. Selected electron-deficient boron Lewis acids catalyze the release of hydrosilanes from cyclohexa-2,5-dien-1-yl-substituted silanes. The two-step process consists of a hydride abstraction to gene…
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Catalytic, Enantioselective Synthesis of Allenyl Boronates Open
A method to achieve enantioselective 1,4-hydroboration of terminal enynes to access allenyl boronates under CuH catalysis is described. The reaction typically proceeds in a highly stereoselective manner and tolerates an array of synthetica…
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Evaluation of Cobalt Complexes Bearing Tridentate Pincer Ligands for Catalytic C–H Borylation Open
Cobalt(II) dichloride complexes supported by a variety of neutral, tridentate pincer ligands have been prepared and, following in situ activation with NaBEt3H, evaluated for the catalytic borylation of 2-methylfuran, 2,6-lutidine, and benz…