2,2‐Difluorovinyl Pinacolborane – A New Versatile Reagent for the Suzuki–Miyaura Reaction

Blahun, Oleksandr P.; Redka, Mykhailo O.; Voitenko, Zoia; Kysil, Andrii I.; Dobrydnev, Alexey V.; Grygorenko, Oleksandr O.

doi:10.1002/ejoc.201901118

Cited by 7 publications

(2 citation statements)

References 52 publications

(10 reference statements)

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“…[39] Similar methods are known to produce alkenylboronates from alkenes including fluorinated olefins. [40] As an alternative to these deprotonation methods that usually require strong bases and anhydrous conditions; a milder, atom economic and straightforward method, consisting in direct borylation through a transition metal-promoted C(sp 2 )À H activation, was developed by the Hartwig Group for the direct photochemically assisted borylation of arenes and terminal alkenes using stoichiometric amounts of some monoboryl complexes of Re, Mn and Fe. [41] Further development of catalytic versions has enabled the preparation of various arylboronates [42,43] and alkenylboronates.…”

Section: Main Preparative Methods Of Alkenylboronates and Arylboronatesmentioning

confidence: 99%

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

et al. 2021

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Organoboron compounds, especially alkenylboronates and arylboronates are highly useful reagents and versatile building blocks in the modern synthetic chemistry toolbox. This review focuses on copper-catalyzed routes to access alkenyl-and arylboronate esters. Various copper salts and ligands have been employed to access them in excellent regio-and stereoselectivity as well as high yields. Both addition and substitution reactions to alkenylboronates have been highlighted based on various methodologies including hydroboration, carboboration, borylative opening of propargyl three-and four-membered rings, dehalogenative borylation of alkenyl bromides and iodides, defluoroborylation of fluoroalkenes and direct C(sp 2 )À H bond activation of alkenes. Preparation of arylboronates involving borylation of aryl halides, C(sp 2 )À H borylation of arenes and cascade 1,3-halogen migration/borylation of 2halostyrenes have been reviewed. Mechanistic aspects of those borylation reactions are discussed briefly.

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Section: Main Preparative Methods Of Alkenylboronates and Arylboronatesmentioning

confidence: 99%

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

et al. 2021

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“…Standard protocols to install gem -difluoroalkenes via carbonyl olefination reactions or defluorination of trifluoromethylated alkenes involve the use of complex starting materials or reagents and suffer from poor selectivity or modest scopes owing to the harsh reaction conditions ( 51 – 57 ). The development of cross-coupling methods has led to gem -difluorovinylating reagents, including 2,2-difluorovinyl pinacolboranes ( 58 ), 2,2-difluorovinylstannanes ( 59 , 60 ), and 2,2-difluorovinyl tosylates ( 61 , 62 ). However, these reagents are not bench stable, and their preparation entails complex synthesis and isolation procedures.…”

Section: Further Synthetic Applicationsmentioning

confidence: 99%

Handling fluorinated gases as solid reagents using metal-organic frameworks

Keasler,

Zick,

Stacy

et al. 2023

Science

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Fluorine is an increasingly common substituent in pharmaceuticals and agrochemicals because it improves the bioavailability and metabolic stability of organic molecules. Fluorinated gases represent intuitive building blocks for the late-stage installation of fluorinated groups, but they are generally overlooked because they require the use of specialized equipment. We report a general strategy for handling fluorinated gases as benchtop-stable solid reagents using metal-organic frameworks (MOFs). Gas-MOF reagents are prepared on gram-scale and used to facilitate fluorovinylation and fluoroalkylation reactions. Encapsulation of gas-MOF reagents within wax enables stable storage on the benchtop and controlled release into solution upon sonication, which represents a safer alternative to handling the gas directly. Furthermore, our approach enables high-throughput reaction development with these gases.

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Tunable Synthesis of Monofluoroalkenes and Gem‐Difluoroalkenes via Solvent‐Controlled Rhodium‐Catalyzed Arylation of 1‐Bromo‐2,2‐difluoroethylene

Xu,

Zhang

et al. 2023

Angewandte Chemie

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Divergent synthesis of fluorine‐containing scaffolds starting from a suite of raw materials is an intriguing topic. Herein, we report the solvent‐controlled rhodium‐catalyzed tunable arylation of 1‐bromo‐2,2‐difluoroethylene. The selection of the reaction solvents provides switchable defluorinated or debrominated arylation from readily available feedstock resources (both arylboronic acids/esters and 1‐bromo‐2,2‐difluoroethylene are commercially available). This switch is feasible because of the difference in coordination ability between the solvent (CH2Cl2 or CH3CN) and the rhodium center, resulting in different olefin insertion. This protocol allows the convenient synthesis of monofluoroalkenes and gem‐difluoroalkenes, both of which are important scaffolds in the fields of medicine and materials. Moreover, this newly developed solvent‐regulated reaction system can be applied to the site‐selective dechlorinated arylation of trichloroethylene. Overall, this study provides a useful strategy for the divergent synthesis of fluorine‐containing scaffolds and provides insight into the importance of solvent selection in catalytic reactions.

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2,2‐Difluorovinyl Pinacolborane – A New Versatile Reagent for the Suzuki–Miyaura Reaction

Cited by 7 publications

References 52 publications

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

Handling fluorinated gases as solid reagents using metal-organic frameworks

Tunable Synthesis of Monofluoroalkenes and Gem‐Difluoroalkenes via Solvent‐Controlled Rhodium‐Catalyzed Arylation of 1‐Bromo‐2,2‐difluoroethylene

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