446311-34-8

Usage

Uses

2-(4''-Methoxy-4-biphenylyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

Upstream product

• 104-92-7 1-bromo-4-methoxy-benzene 
• 99770-93-1 benzene-1,4-diboronic acid bispinacol ester 
• 73852-88-7 2-(4-iodophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 5720-07-0 4-methoxyphenylboronic acid 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 450-39-5 4-(4-fluorophenyl)anisole 
• 73183-34-3 bis(pinacol)diborane 
• 76-09-5 2,3-dimethyl-2,3-butane diol 
• 58743-83-2 4-bromo-4'-methoxylbiphenyl 
• 18158-44-6 4-dimethylamino-4'-methoxybiphenyl 
• 586-77-6 4-bromo-N,N-dimethylaniline 
• 5467-74-3 4-Bromophenylboronic acid 
• 696-62-8 para-iodoanisole 

Downstream Products

• 1447973-44-5 C₁₉H₂₃BO₄ 
• 1447973-73-0 C₁₉H₂₃BO₄ 

Relevant academic research and scientific papers

Photoinduced Deaminative Borylation of Unreactive Aromatic Amines Enhanced by CO2

Herein, direct unreactive C-N borylation of aromatic amines by a photocatalyst was achieved. The C-N borylation of aromatic amines with bis(pinacolato)diboron (B2pin2) proceeded using a pyrene catalyst under light irradiation to afford desired borylated products and aminoborane as a byproduct. The yield of the borylated product improved under a CO2 atmosphere which probably reduced the inhibitory effect of aminoborane. Mechanistic studies suggested that the C-N bond cleavage and C-B bond formation proceeded via a concerted pathway.

Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation

Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.

Development and Mechanistic Studies of Iron-Catalyzed Construction of Csp2-B Bonds via C-O Bond Activation

Herein we describe an iron-catalyzed borylation of alkenyl and aryl carbamates through the activation of a C-O bond. This protocol exhibits high efficiency, a broad substrate scope, and the late-stage borylation of biorelevant compounds, thus providing potential applications in medicinal chemistry. Moreover, this method enables orthogonal transformations of phenol derivatives and also offers good opportunities for the synthesis of multisubstituted arenes. Preliminary mechanistic studies suggest that a FeII/FeIII catalytic cycle via a radical pathway might be involved in the reaction.

COMPOUNDS FOR THE MODULATION OF PROPROTEIN CONVERTASE SUBTILISIN/KEXIN TYPE 9 (PCSK9)

The present disclosure relates to novel compounds capable of binding to PCSK9, thereby modulating PCSK9 biological activity. Also provided are compositions comprising these compounds, methods of preparing the compounds, and methods for use of the compounds in the treatment of PCSK9-related conditions and diseases.

Modular and Selective Arylation of Aryl Germanes (C?GeEt3) over C?Bpin, C?SiR3 and Halogens Enabled by Light-Activated Gold Catalysis

Selective C (Formula presented.) –C (Formula presented.) couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C?BPin, C?SiMe3, C?I, C?Br, C?Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C?Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N2+ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N2+, which requires an alternative photo-redox approach to enable productive couplings.

Suzuki-miyaura cross-coupling of 1,8-diaminonaphthalene (dan)-protected arylboronic acids

We report a Suzuki-Miyaura cross-coupling reaction of 1,8-diaminonaphthalene (dan)-protected arylboronic acids in the presence of KOt-Bu, which does not require the removal of the dan moiety. Notably, the use of aryl-B(dan) in the Suzuki-Miyaura reaction provides a complementary solution to the protodeboronation problems. The base KOt-Bu plays a crucial role for the promotion of these cross-coupling reactions as it enables the formation of a borate salt. This reaction protocol was extended to the one-pot sequential Suzuki-Miyaura cross-coupling reaction of 4-[(pin)B]C6H4-B(dan), wherein the "less reactive" aryl-B(dan) moiety was cross-coupled preferentially.

Orthogonal Nanoparticle Catalysis with Organogermanes

Although nanoparticles are widely used as catalysts, little is known about their potential ability to trigger privileged transformations as compared to homogeneous molecular or bulk heterogeneous catalysts. We herein demonstrate (and rationalize) that nanoparticles display orthogonal reactivity to molecular catalysts in the cross-coupling of aryl halides with aryl germanes. While the aryl germanes are unreactive in LnPd0/LnPdII catalysis and allow selective functionalization of established coupling partners in their presence, they display superior reactivity under Pd nanoparticle conditions, outcompeting established coupling partners (such as ArBPin and ArBMIDA) and allowing air-tolerant, base-free, and orthogonal access to valuable and challenging biaryl motifs. As opposed to the notoriously unstable polyfluoroaryl- and 2-pyridylboronic acids, the corresponding germanes are highly stable and readily coupled. Our mechanistic and computational studies provide unambiguous support of nanoparticle catalysis and suggest that owing to the electron richness of aryl germanes, they preferentially react by electrophilic aromatic substitution, and in turn are preferentially activated by the more electrophilic nanoparticles.

Base-free nickel-catalysed decarbonylative Suzuki–Miyaura coupling of acid fluorides

The Suzuki–Miyaura cross-coupling of organoboron nucleophiles with aryl halide electrophiles is one of the most widely used carbon–carbon bond-forming reactions in organic and medicinal chemistry1,2. A key challenge associated with these transformations is that they generally require the addition of an exogenous base, the role of which is to enable transmetallation between the organoboron nucleophile and the metal catalyst3. This requirement limits the substrate scope of the reaction because the added base promotes competitive decomposition of many organoboron substrates3–5. As such, considerable research has focused on strategies for mitigating base-mediated side reactions6–12. Previous efforts have primarily focused either on designing strategically masked organoboron reagents (to slow base-mediated decomposition)6–8 or on developing highly active palladium precatalysts (to accelerate cross-coupling relative to base-mediated decomposition pathways)10–12. An attractive alternative approach involves identifying combinations of catalyst and electrophile that enable Suzuki–Miyaura-type reactions to proceed without an exogenous base12–14. Here we use this approach to develop a nickel-catalysed coupling of aryl boronic acids with acid fluorides15–17, which are formed in situ from readily available carboxylic acids18–22. This combination of catalyst and electrophile enables a mechanistic manifold in which a ‘transmetallation-active’ aryl nickel fluoride intermediate is generated directly in the catalytic cycle13,16. As such, this transformation does not require an exogenous base and is applicable to a wide range of base-sensitive boronic acids and biologically active carboxylic acids.

LiHMDS-Promoted Palladium or Iron-Catalyzed ipso-Defluoroborylation of Aryl Fluorides

A novel and efficient method for the synthesis of arylboronic acid pinacol esters via a palladium- or iron-catalyzed cross-coupling reaction of aryl fluorides with bis(pinacolato)diboron (B2pin2) in the presence of LiHMDS was developed. The Pd-catalyzed defluoroborylation of fluoroarenes is compatible with a variety of functional groups such as primary and secondary amine, ketone, trifluoromethyl, alkoxy, and boryl. Remarkably, no external ligand is required for enhanced conversion efficiency.

Iron-Catalyzed Borylation of Aryl Chlorides in the Presence of Potassium t-Butoxide

A catalytic amount of an inorganic iron salt such as Fe(acac)3 catalyzes borylation of various aryl and heteroaryl chlorides with bis(pinacolato)diboron, where the presence of potassium t-butoxide is crucially important. The alkoxide is considered to produce in situ an electron-rich iron alkoxide complex as the active species. The reaction requires only an iron salt and potassium t-butoxide as promoters and is easily scalable. The arylboron compound prepared by this reaction can be further coupled in situ with an aryl halide under the Suzuki-Miyaura conditions.