8 research outputs found
Borane-Catalyzed C(sp<sup>3</sup>)âF Bond Arylation and Esterification Enabled by Transborylation
Synthesis of DBpin using Earth-abundant metal catalysis
The synthesis of DBpin was achieved using (EtBIP)CoCl2 or (tBuPNN)FeCl2 as pre-catalysts activated with NaOtBu. (EtBIP)CoCl2 was used as a pre-catalyst for the hydrogen isotope exchange of HBpin with D2, and (tBuPNN)FeCl2 for deuterogenolysis of B2pin2. The one-pot, tandem hydrogenolysis-hydroboration/deuterogenolysis-deuteroboration reaction of terminal alkenes could be catalysed by (tBuPNN)FeCl2 to give alkyl boronic esters
Boron-Catalyzed, Diastereo- and Enantioselective Allylation of Ketones with Allenes
The diastereo- and enantioselective allylation of ketones remains a synthetic challenge, with transition metal catalysis offering the most applied methods. Here, a boron-catalyzed allylation of ketones with allenes is presented. Excellent yield, regioselectivity, and diastereoselectivity were found across functionalized substrates. The reaction was further developed to accommodate an enantioenriched boron catalyst and thus gave asymmetric ketone allylation in good yield, diastereoselectivity, and enantioselectivity. Mechanistic studies supported a hydroborationâallylationâtransborylation pathway.S.P.T. acknowledges the Royal Society for a University Research Fellowship (URF/R/191015). S.P.T. and K.N. thank AstraZeneca and EPSRC for an iCase PhD studentship
AluminiumâCatalyzed C(sp)âH Borylation of Alkynes
Historically used in stoichiometric hydroalumination chemistry, recent advances have transformed aluminium hydrides into versatile catalysts for the hydroboration of unsaturated multiple bonds. This catalytic ability is founded on the defining reactivity of aluminium hydrides with alkynes and alkenes: 1,2âhydroalumination of the unsaturated Ïâsystem. This manuscript reports the aluminium hydride catalyzed dehydroborylation of terminal alkynes. A tethered intramolecular amine ligand controls reactivity at the aluminium hydride centre, switching off hydroalumination and instead enabling selective reactions at the alkyne CâH Ïâbond. Chemoselective CâH borylation was observed across a series of arylâ and alkylâsubstituted alkynes (21 examples). On the basis of kinetic and density functional theory studies, a mechanism in which CâH borylation proceeds by Ïâbond metathesis between pinacolborane (HBpin) and alkynyl aluminium intermediates is proposed
Autonomous execution of highly reactive chemical transformations in the Schlenkputer
We design a modular programmable inert-atmosphere Schlenkputer (Schlenk-line computer) for the synthesis and manipulation of highly reactive compounds, including those that are air and moisture sensitive or pyrophoric. Here, to do this, we constructed a programmable Schlenk line using the Chemputer architecture for the inertization of glassware that can achieve a vacuum line pressure of 1.5âĂâ10â3âmbar, and integrated a range of automated Schlenk glassware for the handling, storage and isolation of reactive compounds at sub-ppm levels of O2 and H2O. This has enabled automation of a range of common organometallic reaction types for the synthesis of four highly reactive compounds: [Cp2TiIII(MeCN)2]+, CeIII{N(SiMe3)2}3, B(C6F5)3 and {DippNacNacMgI}2, which are variously sensitive to temperature, pressure, water and oxygen. Automated crystallization, filtration and sublimation are demonstrated, along with analysis using inline nuclear magnetic resonance or reaction sampling for ultravioletâvisible spectroscopy. Finally, we demonstrate low-temperature reactivity down to â90â°C as well as safe handling and quenching of alkali metal reagents using dynamic feedback from an in situ temperature probe
BâN/BâH Transborylation: borane-catalysed nitrile hydroboration
The reduction of nitriles to primary amines is a useful transformation in organic synthesis, however, it often relies upon stoichiometric reagents or transition-metal catalysis. Herein, a borane-catalysed hydroboration of nitriles to give primary amines is reported. Good yields (48â95%) and chemoselectivity (e.g., ester, nitro, sulfone) were observed. DFT calculations and mechanistic studies support the proposal of a double BâN/BâH transborylation mechanism
Group 13 exchange and transborylation in catalysis
Catalysis is dominated by the use of rare and potentially toxic transition metals. The main group offers a potentially sustainable alternative for catalysis, due to the generally higher abundance and lower toxicity of these elements. Group 13 elements have a rich catalogue of stoichiometric addition reactions to unsaturated bonds but cannot undergo the redox chemistry which underpins transition-metal catalysis. Group 13 exchange reactions transfer one or more groups from one group 13 element to another, through Ï-bond metathesis; where boron is both of the group 13 elements, this is termed transborylation. These redox-neutral processes are increasingly being used to render traditionally stoichiometric group 13-mediated processes catalytic and develop new catalytic processes, examples of which are the focus of this review