Metal‐Catalyzed Borylation of CH and CHalogen Bonds of Alkanes, Alkenes, and Arenes for the Synthesis of Boronic Esters

Nickel‐Catalyzed Enantioconvergent Borylation of Racemic Secondary Benzylic Electrophiles

“…Aware of the importance of enantioenriched organoboron compounds, we chose to explore the possibility that a boron reagent might serve as the first effective heteroatom-based nucleophile in nickel-catalyzed enantioconvergent cross-couplings. [8,9,10,11] Herein, we establish the viability of this approach (Figure 1b), specifically, we report a nickel/pybox-catalyzed borylation that provides enantioenriched boronic esters in good enantiomeric excess from an array of racemic secondary benzylic chlorides [Eq. (1)].…”

Additive- and Metal-Free, Predictably 1,2- and 1,3-Regioselective, Photoinduced Dual C–H/C–X Borylation of Haloarenes

“…5 Regioselective installation of two boryl groups in the aromatic ring is challenging and is usually accomplished by borylation of the preinstalled C–X bonds using transition metal catalysis 6,7 or by generating dimagnesiated or dilithiated intermediates. 8 Alternatively, Rh- and Ir-catalyzed C–H-borylation 9 has also been used to prepare diborylarenes and related PBAs.…”

“…Aromatic di- and polyboronic acids (PBAs) are valuable organoboron materials with important roles in synthetic organic chemistry, molecular self-assembly, anion recognition, molecular optoelectronics, and materials science . Regioselective installation of two boryl groups in the aromatic ring is challenging and is usually accomplished by borylation of the preinstalled C–X bonds using transition metal catalysis , or by generating dimagnesiated or dilithiated intermediates . Alternatively, Rh- and Ir-catalyzed C–H borylation has also been used to prepare diborylarenes and related PBAs .…”

Aryloxymethyltrifluoroborates for Rhodium-Catalyzed Asymmetric Conjugate Arylation. o-Methoxyarylation through 1,4-Rhodium Shift

“…The arylboron reagents, which possess an aryl carbon–boron bond, are prepared by the borylation of Ar–M (M = Li, Mg) reagents in most cases. Borylation of Ar–X (X = halides, triflate) and Ar–H by transition-metal-catalyzed reaction with diboron reagents is another preparation method which has been developed recently …”