Tri(boryl)alkanes and Tri(boryl)alkenes: The Versatile Reagents

Salvadó, Oriol; Fernández, Elena

doi:10.3390/molecules25071758

Cited by 29 publications

(30 citation statements)

References 36 publications

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“…It has become one of the most important methodologies to synthesize complex molecules from simple building blocks. Organoboronate derivatives are widely employed in the construction of C–O, C–N, and C–X bonds and as such are significant feedstocks for the synthesis of pharmaceuticals, agrochemicals, liquid crystals, and organic light-emitting diodes. − The boronic acid motif appears directly in boron-containing drugs, such as bortezomib (Velcade), − an anticancer agent, and tavaborole (Kerydin), an antifungal agent, − in biologically related sensors, e.g. for sugars and hydrogen peroxide, and as building blocks for novel covalent organic framework materials for gas storage. − …”

Section: Introductionmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon−boron bond into a carbon−X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row dblock transition metals have become increasingly widely used as catalysts for the formation of a carbon−boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon−boron bonds.

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Section: Introductionmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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“…e 1,4-conjugate addition product was not detected; the 1,2-addition products (via Boron-Wittig reaction) were observed instead reported deborylative conjugate addition of benzylic triborons 9 collectively suggest that in comparison to the benzylic group the presence of an additional boryl group provides greater soft nucleophilic character to the α-boryl stabilized anion. Multiborylated alkanes such as 1,1,2-tris-borons 19 have been previously shown to be valuable building blocks for site-selective installation of molecular diversity via sequential transformations of boryl groups. The successful conjugate addition of 3i allows access to multifunctional tris-borons having ketones as additional synthetic handles.…”

Section: One-pot Diboron Conjugate Addition-oxidation γ-Keto Acylboronmentioning

confidence: 99%

Boron-promoted Deprotonative Conjugate Addition: Development of Geminal diborons as Versatile Soft Pronucleophiles and Acyl An-ion Equivalents

Wang

Lin

Santos

et al. 2022

Preprint

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Conjugate addition of α-boron stabilized carbanions is an underexplored reaction modality. Existing methods require deborylation of geminal di/triboryl alkanes and/or the presence of additional activating groups. We report the 1,4-addition of α,α-diboryl carbanions generated via deprotonation of corresponding geminal diborons. The methodology enabled a general route to highly substituted and synthetically useful γ,γ-diboryl ketones. The development of geminal diborons as soft pronucleophiles also enabled their use as acyl anion equivalents via one-pot tandem conjugate addition-oxidation sequence.

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“…Their activation by deprotonation or deborylation strategies has been also applied in the construction of new carbon‐carbon and carbon‐heteroatom bonds. Both the synthetic procedures and the limitations have been collected in a recent review [90] …”

Section: Reactivity Of Borata‐alkene Compoundsmentioning

confidence: 99%

Borata‐Alkene Species as Nucleophilic Reservoir

2021

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α‐Monoboryl anions show remarkable stability due to the valence deficiency of the adjacent three‐coordinate boron center and can be expressed as its resonance form, the borata‐alkene systems [R2B=CH2]−. The diversity of synthetic approaches as well as the properties of the C=B bond are disclosed in this review, dealing with both electronic and structural properties of the boryl moieties involved. Full characterization in solid state by X‐ray diffraction demonstrated the short distances between B and C, as a consequence of the boron ylide character in the boron‐stabilized carbanions. This review includes a collection of C−B length distances as well as 11B NMR data that can be useful for diagnostic evidence of the partial boron‐carbon double‐bond character. Natural bond orbital (NBO) analysis on DFT computed structures also supports and justifies the borata‐alkene character. The reactivity of the C=B bond acting as nucleophilic synthon is unveiled through extensive electrophilic trapping examples. The homologation protocols with diborylmethane, via single carbon chain extension, involves a facile introduction of the C(sp3)−B bonds, which can be subsequently transformed into functionalized target products, containing C−O, C−N or C−C bonds.

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Tri(boryl)alkanes and Tri(boryl)alkenes: The Versatile Reagents

Cited by 29 publications

References 36 publications

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Boron-promoted Deprotonative Conjugate Addition: Development of Geminal diborons as Versatile Soft Pronucleophiles and Acyl An-ion Equivalents

Borata‐Alkene Species as Nucleophilic Reservoir

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