Recent advances in the synthesis and reactivity of MIDA boronates

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(96), P. 13298 - 13316

Published: Jan. 1, 2022

MIDA boronates have been widely applied as building blocks in the synthesis of natural products and pharmaceuticals precursors. This review highlights recent advances provides a comprehensive summary their reactivity.

Language: Английский

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Zr-Catalyzed Assembly of 1,1,1-Triborylalkanes from Alkenes and HBpin

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 10, 2025

Multiboronated compounds play more and significant roles in the chemical community, 1,1,1-triborylalkanes have emerged as versatile building blocks organic synthesis. However, efficient strategies for assembly of such are very rare. A general atom-economical synthesis from various alkenes with pinacolborane (HBpin) is reported first time. The success this transformation relies on use commercially available Schwartz reagent (Cp2ZrHCl) a catalyst, enabling sequential dehydrogenative borylation hydroboration. This reaction demonstrates excellent selectivity, high yields, broad functional group tolerance. Mechanistic investigations reveal that process begins two consecutive borylations catalyzed by zirconium, producing 1,1-diborylalkene intermediate, which subsequently undergoes hydroboration HBpin to afford 1,1,1-triborylalkanes. Notably, approach allows remote 1,1,1-triboration internal alkenes.

Language: Английский

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Progress in the Electrochemical Synthesis of Organoboron Compounds

Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(4)

Published: March 8, 2023

Abstract Organoboron is a class of compounds widely used in organic synthesis, pharmaceuticals, material science, sensors, and so on. Therefore, the development efficient selective electrochemical methods to synthesize organoboron has attracted much interest as an emerging sustainable technique synthesis. Here, we summarized research on borylations, including electrochemically driven borylation arenes, alkanes, aryl, or alkyl halides, activated carboxylic acids etc., based direct electrolysis metal‐free organocatalysis. We focus reaction mechanisms involved single‐electron transfer other radical processes. believe that this review will inspire electrochemists discover more transformations expand field borylation.

Language: Английский

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Two Directing Groups Used for Metal Catalysed Meta‐C−H Functionalisation Only Effect Ortho Electrophilic C−H Borylation

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(44)

Published: Oct. 21, 2022

Two templates used in meta-directed C-H functionalisation under metal catalysis do not direct meta-C-H borylation electrophilic conditions. Using BCl3 only Lewis adduct formation with basic sites the template is observed. While combining BBr3 and containing an amide linker led to directed ortho borylation, no pyridyl meta borylation. The selective for of aniline derived unit template, phenylacetyl ring - which would also form a six membered boracycle In absence other aromatics on rings can be achieved. meta-borylation using two indicates higher barrier relative suggests that bespoke enabling may required.

Language: Английский

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Understanding the Mechanism and Selectivity of 1,1-Diborylalkanes from Alkenes Catalyzed by a Zirconium Complex

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(27), P. 10854 - 10864

Published: June 26, 2023

The synthesis of 1,1-diborylalkanes from readily available alkenes is an appealing method. density functional theory (DFT) method was employed to investigate the reaction mechanism 1,1-diborylalkanes, which synthesized and a borane, catalyzed by zirconium complex Cp2ZrCl2. entire divided into two cycles: dehydrogenative boration form vinyl boronate esters (VBEs) hydroboration VBEs. This article focuses on cycle elaborates role reducing reagents in equilibrium self-contradictory reactivity (dehydrogenative hydroboration). H2 HBpin pathways were investigated as process. calculated results showed that it more advantageous use agent (path A). Furthermore, σ-bond metathesis rate-determining step (RDS) with energetic span 21.4 kcal/mol. consistent balance proposed experiment. modes process also discussed. These analyses revealed origin selectivity this reaction, needs overcome strong interaction between Zr metal. Meanwhile, different positions σ(H1-H2) → σ*(Zr1-C1) overlap these findings have implications for catalyst design application.

Language: Английский

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Selective Transformations Mediated by Group 4 Metal Cyclopentadienyl Complexes

Topics in organometallic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 117 - 160

Published: Jan. 1, 2024

Language: Английский

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