325142-84-5

Usage

Uses

Used in Pharmaceutical Industry:
2-(3-METHOXYLOXYPHENYL)-4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLANE is used as a key intermediate compound for the synthesis of inhibitors targeting Transforming Growth Factor-beta 1 (TGF-β1) and Activin A signaling pathways. These inhibitors play a crucial role in regulating cellular processes such as cell proliferation, differentiation, and migration, which are often dysregulated in various diseases, including cancer. By modulating these signaling pathways, the compound can potentially be used in the development of therapeutic agents for treating diseases associated with abnormal TGF-β1 and Activin A signaling.

InChI:InChI=1/C9H13BO4S/c1-7(2)15(13,14)9-5-3-8(4-6-9)10(11)12/h3-7,11-12H,1-2H3

Upstream product

• 2845-89-8 1-chloro-3-methoxy-benzene 
• 73183-34-3 bis(pinacol)diborane 
• 100-66-3 methoxybenzene 
• 25015-63-8 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane 
• 2398-37-0 3-methoxyphenyl bromide 
• 766-85-8 3-methoxy-1-iodobenzene 
• 745783-97-5 triethyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 10365-98-7 3-methoxyphenylboronic acid 
• 1245824-47-8 4-methoxy-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl N,N-diethylcarbamate 
• 85630-18-8 N,N-diethyl-O-(4-methoxyphenyl)carbamate 
• 36651-92-0 1-[2-(3-methoxyphenyl)diazen-1-yl]pyrrolidine 
• 536-90-3 m-Anisidine 
• 450412-22-3 1-bromo-2-iodo-3-methoxybenzene 

Downstream Products

• 1011472-11-9 3-(3-methoxyphenyl)-N-phenylimidazo[1,2-a]pyrazin-8-amine 
• 1130489-32-5 C₂₂H₁₉N₃O 
• 1256781-58-4 2-(2-bromo-5-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 1256781-69-7 2-(2-iodo-5-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 1256781-73-3 2-(2-chloro-5-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 53906-83-5 3'-methoxyflavone 
• 150-19-6 O-methylresorcine 
• 73910-79-9 1-methoxy-6-methyl-9H-carbazole 
• 5234-30-0 glycozoline 
• 3001-15-8 4,4'-diiodobiphenyl 

Relevant academic research and scientific papers

Palladium-catalyzed borylation of aryl bromides and chlorides using phosphatrioxa-adamantane ligands

Catalysts based on the combination of Pd(OAc)2 and the electron-deficient phosphatrioxa-adamantane ligands are described for borylation of aryl bromides and chlorides. Catalytic evaluation of a small library of phosphatrioxa-adamantane ligands provided some insights on the preferred ligand steric profile for borylation reactions. The corresponding aryl boronate esters were accessed under mild conditions (25–70 °C) and isolated in high yields (up to 96%).

Mono-Phosphine Metal-Organic Framework-Supported Cobalt Catalyst for Efficient Borylation Reactions

We report a metal-organic framework (MOF) supported monoligated phosphine-cobalt complex, which is an active heterogeneous catalyst for aromatic C?H borylation and alkene hydroboration. The mono(phosphine)-Co catalyst (MOF?P?Co) was prepared by metalation of a porous triarylphosphine-functionalized MOF (MOF?P) with CoCl2 followed by activation with NaEt3BH. The MOF catalyst has a broad substrate scope with excellent functional group tolerance to afford arene- and alkyl-boronate esters in excellent yields and selectivity. MOF?P?Co gave a turnover number (TON) of 30,000 and could be recycled and reused at least 13 times in arene C?H borylation. Importantly, the attempt to prepare the homogeneous control (Ph3P?Co) using triphenylphosphine was unsuccessful due to the facile disproportionation reactions or intermolecular ligand exchanges in the solution. In contrast, the site isolation of the active mono(phosphine)-Co species within the MOF affords the robust and coordinatively unsaturated metal complexes, allowing to explore their catalytic properties and the reaction mechanism.

Unreactive C-N Bond Activation of Anilines via Photoinduced Aerobic Borylation

Unreactive C-N bond activation of anilines was achieved by photoinduced aerobic borylation. A diverse range of tertiary and secondary anilines were converted to aryl boronate esters in moderate to good yields with wide functional group tolerance under simple and ambient photochemical conditions. This transformation achieved the direct and facile C-N bond activation of unreactive anilines, providing a convenient and practical route transforming widely available anilines into useful aryl boronate esters.

Engaging Ag(0) single atoms in silver(I) salts-mediated C-B and C-S coupling under visible light irradiation

Silver(I) salts were found active in the borylation and sulfenylation of aryl iodides under visible light irradiation. The optimized borylation protocol using AgF did not need any additive, operated under very mild conditions, and well tolerated a broad scope of substrates and boron sources. Formation of Ag(0) single atoms (AgSAs) during the borylation reactions was examined using high-angle annular dark field aberration-corrected scanning transmission electron microscope (HAADF AC-STEM) and electron paramagnetic resonance (EPR). The activities of the silver(I) salts were affected by the anions and could be associated with their abilities in formation of AgSAs during the reactions. Kinetic studies showed that the deiodination rate was linearly correlated with the loading of AgSAs, and hence AgSAs were the true catalytic centers for the 1e?-reduction of the C-I moieties. The oxidation state of AgSAs kept 0 in both the resting and the working states. A “work-in-tandem” mechanism involving AgSAs as the catalytic centers and AgNPs as the light absorber to achieve the borylation of aryl iodides under visible light irradiation is proposed. The current approach not only provides an alternative system for borylation and sulfenylation of aryl iodides, but also reveals a new activity of silver(I) salts involving AgSAs under visible light irradiation.

Zinc Complexes with an Ethylene-Bridged Bis(β-diketiminate) Ligand: Syntheses, Structures, and Applications as Catalysts in the Borylation of Aryl Iodides

A dinucleating bis(β-diketiminate) ligand with a flexible bridge has been employed to synthesize zinc complexes. The ligand, abbreviated H2L (H2L = N-(4-((2-((4-((2,6-diisopropylphenyl)imino)pent-2-en-2-yl)amino)ethyl)imino)pent-2-en-2-yl)-2,6-diisopropylaniline), was deprotonated with ZnEt2 to afford [LZn2Et2] (1). Reactions of 1 with 2 equiv of BnOH and nBuOH, respectively, gave access to [LZn2(OBn)2]·C6H14 (2·C6H14) and [LZn2(OnBu)2] (3). Treatment of 1 with 2 equiv of I2 in THF produced [LZn2I2(THF)2]·2THF (4·2THF). X-ray single-crystal diffraction analyses revealed that they are all heteroleptic bimetallic compounds with two metal centers being chelated by one ligand set. The structurally similar compounds 1 and 4·2THF possess approximate C2 symmetry, with two β-diketiminate units being arrayed in head-to-tail antiparallel mode. Thus, the molecular structures of 1 and 4·2THF exhibit a seesaw-like topology. The structures of 2·C6H14 and 3 are almost identical, in which two zinc atoms are shared by two ZnN2C3 six-membered rings, two Zn2ON2C2 seven-membered rings, and one Zn2O2 four-membered ring. Therefore, the metal cores of 2·C6H14 and 3 display a crownlike topology. All complexes are catalytically active for the borylation of aryl iodides with B2Pin2 (B2Pin2 = 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis(1,3,2-dioxaborolane). Complex 1 shows higher activity in comparison to 2, 3, and 4·2THF. The borylation reactions catalyzed by 1 could proceed under mild conditions and can be applied to a series of substrates with high functional group generality. This methodology thus represents a novel use of β-diketiminate zinc complexes for C-I borylation.

Evaluation of the role of graphene-based Cu(i) catalysts in borylation reactions

Carbon-supported catalysts have been considered as macromolecular ligands which modulate the activity of the metallic catalytic center. Understanding the properties and the factors that control the interactions between the metal and support allows a fine tuning of the catalyzed processes. Although huge effort has been devoted to comprehending binding energies and charge transfer for single atom noble metals, the interaction of graphenic surfaces with cheap and versatile Cu(i) salts has been scarcely studied. A methodical experimental and theoretical analysis of different carbon-based Cu(i) materials in the context of the development of an efficient, general, scalable, and sustainable borylation reaction of aliphatic and aromatic halides has been performed. We have also examined the effect of microwave (MW) radiation in the preparation of these type of materials using sustainable graphite nanoplatelets (GNP) as a support. A detailed analysis of all the possible species in solution revealed that the catalysis is mainly due to an interesting synergetic Cu2O/graphene performance, which has been corroborated by an extensive theoretical study. We demonstrated through DFT calculations at a high level of theory that graphene enhances the reactivity of the metal in Cu2O against the halide derivative favoring a radical departure from the halogen. Moreover, this material is able to stabilize radical intermediates providing unexpected pathways not observed using homogeneous Cu(i) catalysed reactions. Finally, we proved that other common carbon-based supports like carbon black, graphene oxide and reduced graphene oxide provided poorer results in the borylation process.

One-pot synthesis of Ag-Cu-Cu2O/C nanocomposites derived from a metal-organic framework as a photocatalyst for borylation of aryl halide

Mixed metal-metal oxide/C (Ag-Cu-Cu2O/C) nanocomposites were synthesized by the heat treatment of a metal-organic framework under a N2 flow using the one-pot synthesis method. The as-prepared nanocomposites were characterized using a range of techniques,

Cross-Coupling through Ag(I)/Ag(III) Redox Manifold

In ample variety of transformations, the presence of silver as an additive or co-catalyst is believed to be innocuous for the efficiency of the operating metal catalyst. Even though Ag additives are required often as coupling partners, oxidants or halide scavengers, its role as a catalytically competent species is widely neglected in cross-coupling reactions. Most likely, this is due to the erroneously assumed incapacity of Ag to undergo 2e? redox steps. Definite proof is herein provided for the required elementary steps to accomplish the oxidative trifluoromethylation of arenes through AgI/AgIII redox catalysis (i. e. CEL coupling), namely: i) easy AgI/AgIII 2e? oxidation mediated by air; ii) bpy/phen ligation to AgIII; iii) boron-to-AgIII aryl transfer; and iv) ulterior reductive elimination of benzotrifluorides from an [aryl-AgIII-CF3] fragment. More precisely, an ultimate entry and full characterization of organosilver(III) compounds [K]+[AgIII(CF3)4]? (K-1), [(bpy)AgIII(CF3)3] (2) and [(phen)AgIII(CF3)3] (3), is described. The utility of 3 in cross-coupling has been showcased unambiguously, and a large variety of arylboron compounds was trifluoromethylated via [AgIII(aryl)(CF3)3]? intermediates. This work breaks with old stereotypes and misconceptions regarding the inability of Ag to undergo cross-coupling by itself.

Synthesis of arylboronates via the Pd-catalyzed desulfitative coupling reaction of sodium arylsulfinates with bis(pinacolato)diboron

The desulfitative borylation reaction of sodium arylsulfinates with bis(pinacolato)diboron or bis(neopentylglycolato)diboron under palladium catalysis has been developed, allowing selective C-B bond formation to give arylboronates with a range of functional groups in moderate to good yields under mild reaction conditions. A gram-scale preparation as well as the cascade Suzuki-Miyaura cross-coupling of arylboronates demonstrated the potential practical utility in organic synthesis.

The functionalization of benzene by boranes using trispyrazolylborate complexes

The catalytic C[sbnd]H activation and borylation of arenes by trispyrazolylborate complexes is reported. Trispyrazolylborate rhodium and iridium complexes have been previously shown to activate a variety of C[sbnd]H bonds. Here, we show the catalytic borylation of arenes by the trispyrazolylborate ethylene complexes Tp'Rh(C2H4)2, and Tp'Ir(C2H4)2.