Mononuclear nickel and cobalt boryl complexes have been prepared via sigma-bond metathesis reactions and in the case of nickel, an intermediate comprised of a Lewis acid-base type adduct has been experimentally detected by (31)P NMR spectroscopy and its structure probed by DFT calculations.
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http://dx.doi.org/10.1039/b912040h | DOI Listing |
The selective amination of aromatic C-H bonds is a powerful strategy to access aryl amines, functionalities found in many pharmaceuticals and agrochemicals. Despite advances in the field, a platform for the direct, selective C-H amination of electronically diverse (hetero)arenes, particularly electron-deficient (hetero)arenes, remains an unaddressed fundamental challenge. In addition, many (hetero)arenes present difficulty in common selective pre-functionalization reactions, such as halogenation , or metal-catalyzed borylation and silylation .
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January 2025
Organic Chemistry, Saarland University, Campus Building C4.2, D-66123 Saarbruecken, Germany.
Matteson homologation, a successive extension of chiral boronic esters, is perfectly suited for the synthesis of complex molecular structures containing several stereogenic centers. The "classical version" allows the introduction of various functional groups in a 1,2--configuration. The absolute configuration is determined by the choice of the chiral auxiliary, which can be used to introduce several stereogenic centers.
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January 2025
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University Lanzhou 730000 Gansu China
Substantial advancements have been achieved in the field of photocatalytic borylation utilizing 4c-7e Lewis base-boryl radicals. However, the utilization of 3c-5e neutral boryl radicals for C-B bond formation remains relatively underexplored due to their inherent instability. In this study, we successfully demonstrated the direct construction of C-B bonds using sodium tetraarylborate as a key reagent.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Max-Planck-Institut für Kohlenforschung, 45470, Mülheim/Ruhr, Germany.
Ynamides, when reacted with H or HBpin in the presence of [Cp*RuCl], convert into chiral-at-metal Fischer carbenes by regioselective gem-hydrogenation or gem-hydroboration of the polarized triple bond, respectively. gem-Hydroboration concomitantly affords a carbogenic borylated stereocenter adjacent to the ruthenium carbene unit, the configuration of which can be controlled using an Evans auxiliary. These are the first examples of asymmetric gem-addition reactions to alkynes known in the literature; representative pianostool ruthenium carbene complexes formed by this unconventional route were characterized by crystallographic and spectroscopic means.
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December 2024
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK
The reaction chemistry of an unprecedented 'inorganic cumulene' - featuring a five-atom BNBNB chain - towards C[double bond, length as m-dash]O (and related) multiple bonds is disclosed. In marked contrast to related all-carbon systems, the intrinsic polarity of the BNBNB chain (featuring electron-rich nitrogen and electron-deficient boron centres) enables metathesis chemistry with electrophilic heteroallenes such as CO and with organic carbonyl compounds. Transfer of the borylimide unit to [CO], [CS], [PP{(NDippCH)}] and [C(H)Ph] moieties generates (boryl)N[double bond, length as m-dash]C[double bond, length as m-dash]X systems (X = O, S, PP{(NDippCH)}, C(H)Ph), driven thermodynamically by B-O bond formation.
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