4-vinylphenylboronate MIDA ester - ≥97% , CAS No.1422172-82-4

CAS: 1422172-82-4 Cat. No.: V774960 Formula: C₁₃H₁₄BNO₄ Peso molecolare: 259.07 PubChem CID: 162422665

QUALITÀ & PUREZZA ≥97%

Synonyms

4-Methyl-2,6-dioxo-8-(4-vinylphenyl)hexahydro-[1,3,2]oxazaborolo[2,3-b][1,3,2]oxazaborol-4-ium-8-uide

Storage

Store at 2-8°C,Protected from light,Argon charged

Shipped In

Wet ice

Specifiche

Sinonimi

4-Methyl-2,6-dioxo-8-(4-vinylphenyl)hexahydro-[1,3,2]oxazaborolo[2,3-b][1,3,2]oxazaborol-4-ium-8-uide

Specifiche e purezza

≥97%

Condizioni di conservazione di stoccaggio

Store at 2-8°C,Protected from light,Argon charged

Spedito in

Wet ice

Questo prodotto richiede spedizione a catena fredda. I servizi di terra e altri servizi economici non sono disponibili.

Purezza

≥97%

Nomi e identificatori

Sorrisi canonici

[B-]12([N+](CC(=O)O1)(CC(=O)O2)C)C3=CC=C(C=C3)C=C

IUPAC Name

1-(4-ethenylphenyl)-5-methyl-2,8-dioxa-5-azonia-1-boranuidabicyclo[3.3.0]octane-3,7-dione

InChIKey

BBBFUSCXYALCSC-UHFFFAOYSA-N

INCHI

1S/C13H14BNO4/c1-3-10-4-6-11(7-5-10)14-15(2,8-12(16)18-14)9-13(17)19-14/h3-7H,1,8-9H2,2H3

PubChem CID

162422665

Peso molecolare

259.07

Proprietà chimiche e fisiche

• Sensibilità: light sensitive

Application Protocols

No assay or bioanalytical application protocols are provided for this synthetic reagent. For chemical use, see Reaction Conditions and Application notes regarding deprotection and cross-coupling setups. Any procedural details should be adapted to scale, substrate, and catalytic system, with optimization guided by small-scale trials.

Biological Roles

This compound is a synthetic organic building block (aryl MIDA boronate) and is not intended for biological pathway studies.

• Intrinsic biological role: none established; MIDA boronates serve as protected forms of boronic acids for chemical synthesis.
• Biochemical reactivity: the boron center is masked within a cyclic diester and does not engage in typical boronic acid interactions (e.g., with diols) until deprotected under basic or hydrolytic conditions.
• Use context: in medicinal chemistry workflows, such building blocks are used to assemble screening compounds and SAR series via cross-coupling, but the reagent itself is not a biological probe.

Research Use Note: For research use only (per Product Data). Not for human or animal diagnostic or therapeutic applications.

Buffer Applications

Not typically applicable. 4-vinylphenylboronate MIDA ester is an organic synthesis building block rather than a buffering agent. It does not serve as a pH buffer in aqueous systems. For relevant information, refer to Reaction & Applications, Synthetic Utility, and Reaction Conditions sections for its use in cross-coupling workflows.

Green Alternatives

Greener considerations focus on the process solvents and bases used with this building block, as the reagent itself is a solid intermediate.

• Solvent choices (greener substitutions):
  • Replace dioxane with 2-methyltetrahydrofuran (2-MeTHF) or cyclopentyl methyl ether (CPME), which are bio-based or have improved safety profiles and enable efficient Suzuki couplings.
  • Use ethanol/water or isopropanol/water mixtures for in situ deprotection and coupling when compatible with catalyst/ligand and substrate solubility.
• Bases and aqueous systems:
  • Favor K2CO3, Na2CO3, or K3PO4 in water-rich media over strong hydroxides when feasible to minimize caustic waste and control MIDA hydrolysis.
• Energy and workup:
  • Conduct couplings at moderate temperatures (50–80 °C) with active catalysts to reduce energy input; employ aqueous phase separations to minimize halogenated solvent use.

Illustrative comparison (general):

• Dioxane/H2O vs 2-MeTHF/H2O
  • Safety: dioxane is a probable carcinogen with peroxide risk; 2-MeTHF has better toxicity profile and lower miscibility with water aiding separations.
  • Performance: 2-MeTHF often matches or exceeds rates for Suzuki couplings with appropriate ligation; water compatibility may require surfactant or phase-transfer strategies.

Trade-offs: Greener solvents can alter solubility or catalyst speciation; minor re-optimization (ligand/base loading, temperature) is commonly required.

Pharmaceutical Uses

No excipient or pharmacopeial status is provided for this item. It is supplied for research use only as a synthetic intermediate.

• Potential role in pharma R&D (general): employed to assemble aryl-containing scaffolds via Suzuki–Miyaura coupling and related transformations during lead discovery and library synthesis. The para-vinyl substituent offers further diversification by olefin functionalization.
• Formulation/excipient use: none indicated; not used as a dosage-form component.

Always segregate research-grade materials from GMP operations. For any process development toward regulated manufacturing, obtain full specifications, impurity profiles, and method validations via an approved quality pathway.

Physical Properties

Item-specific values are not provided in the Product Data. For precise numerical specifications, consult the CoA/SDS.

• Appearance: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular weight: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular formula: Not specified for this item; refer to CoA/Spec Sheet.
• Melting point, boiling point, density, refractive index: Not specified for this item; refer to CoA/Spec Sheet.

General/literature characteristics for aryl MIDA boronates (informational):

• Physical state: typically crystalline solids with good bench stability relative to free boronic acids.
• Solubility profile: often soluble in polar aprotic organic solvents (e.g., THF, dioxane, DMF, DMSO, acetonitrile, CH2Cl2) and variably soluble in less polar media (EtOAc, toluene). Low aqueous solubility before hydrolysis; solubility increases under basic aqueous conditions upon MIDA deprotection to the boronate/boronic acid.
• Volatility: negligible; handled as a non-volatile solid.
• Stability: robust to air and moisture compared with pinacol boronates or free boronic acids; slow hydrolysis under strong aqueous base liberates the corresponding boronic acid (literature behavior of MIDA boronates).

These general properties are provided for planning purposes only and are not item-specific specifications.

Quality and Grades

• Grade/purity: Not specified for this item; refer to CoA/Spec Sheet for assay, residual solvent profile, and chromatographic purity.

Context for this compound class:

• MIDA boronates are typically supplied as research-grade building blocks optimized for stability and performance in cross-coupling. High HPLC purity and low inorganic residue facilitate palladium-catalyzed reactions.
• Stabilizer content: None indicated in Product Data. If stabilizers or inhibitors are present (e.g., for vinyl polymerization suppression), they would be listed on the CoA. In their absence, best practice is inert-atmosphere storage as provided (argon charged).
• What grade implies in practice:
  • Research grade: suitable for method development and routine synthesis.
  • HPLC grade (if specified): low UV background and trace metals to minimize catalytic poison—Not specified for this item; refer to CoA/Spec Sheet.
• Batch-specific documentation: Review CoA for identity confirmation (NMR, MS), purity, and any residual catalyst/metal data when critical for catalytic transformations.

Takeaway: Use the CoA to set acceptance criteria for Suzuki–Miyaura couplings or iterative coupling workflows, especially when trace water/metal content and vinyl integrity are mission-critical.

Reaction and Applications

4-vinylphenylboronate MIDA ester is a stable, masked boronic acid tailored for cross-coupling and building-block assembly.

Key application families (general/literature):

• Suzuki–Miyaura cross-coupling: After hydrolysis to the corresponding 4-vinylphenylboronic acid (or via in situ transesterification), couples with aryl/vinyl halides and pseudohalides to forge biaryl and aryl–vinyl bonds. The para-vinyl substituent enables orthogonal diversification (e.g., Heck, hydroboration, epoxidation) post-coupling.
• Iterative/programmable synthesis: MIDA boronates provide temporal masking, enabling sequences of selective couplings and deprotections with high functional-group tolerance (Burke-type protocols).
• One-pot deprotect–couple: Basic aqueous conditions (e.g., NaOH, Na2CO3, or aqueous amines) liberate the boronic acid; Pd(0) catalysts (e.g., Pd(PPh3)4, Pd(dppf)Cl2) then effect coupling in mixed aqueous–organic media.
• Polymer/monomer synthesis: The para-vinyl motif allows radical polymerization or thiol–ene reactions to append the MIDA boronate onto materials, then unmask boron for post-polymer functionalization.

Practical notes:

• Maintain inert atmosphere as supplied; oxygen and moisture are tolerated to a degree but can slow catalysis or induce side reactions of the vinyl group under radical conditions.
• Choose base strength to control deprotection rate: strong base for rapid unmasking; milder bases for slower release to match catalyst turnover.
• Monitor by LC–MS or 11B/1H NMR to track MIDA hydrolysis and coupling progress.

Reaction Conditions

General conditions drawn from literature for aryl MIDA boronates; optimize for your substrate set.

• In situ deprotection + Suzuki–Miyaura coupling:

  • Solvent: 1,4-dioxane/H2O (3:1 to 1:1), THF/H2O, or 2-MeTHF/H2O (green alternative).
  • Base: Na2CO3 or K2CO3 (2–3 equiv); stronger base (NaOH) accelerates MIDA hydrolysis if required.
  • Catalyst: Pd(PPh3)4 (1–3 mol%), Pd(dppf)Cl2·DCM (2–5 mol%), or XPhos/SPhos-ligated Pd sources for challenging aryl chlorides.
  • Temperature/time: 50–90 °C, 2–16 h depending on electrophile reactivity and solubility.

• Pre-deprotection then coupling:

  • Hydrolyze MIDA boronate with aqueous base (e.g., 1–2 M NaOH or K3PO4 in MeOH/H2O or THF/H2O) at rt–50 °C until complete (monitor by TLC/LC–MS), then perform standard Suzuki conditions with the isolated/aqueous-phase boronic acid.

• Vinyl functionalization on the product arene (post-coupling options):

  • Heck reaction: Pd(OAc)2/phosphine ligand, base (Et3N or K2CO3), DMF or toluene, 80–130 °C.
  • Hydroboration–oxidation: BH3·THF or 9-BBN at 0–25 °C; oxidative workup (H2O2/NaOH) to give benzylic alcohols.
  • Olefin metathesis: Grubbs/Hoveyda catalysts in DCM or toluene, rt–60 °C.

Notes:

• Oxygen/moisture: While MIDA boronates are robust, maintain inert conditions for Pd-catalyzed steps.
• Bases containing fluoride (KF, CsF) can accelerate transmetalation for some systems but may affect MIDA integrity; evaluate case-by-case.
• Expected yields: substrate- and catalyst-dependent; consult primary literature for analogous aryl MIDA boronate couplings.

Safety and Handling

Always handle according to your institution’s chemical hygiene plan and the product SDS.

• GHS classification, signal word, pictograms, H-statements: Not specified for this item; refer to SDS for authoritative information.
• Anticipated hazards (general for organoboron MIDA esters): may cause eye/skin irritation and irritation of the respiratory tract if dusts are generated. Avoid inhalation of particulates and contact with skin/eyes.
• Storage conditions (Product Data): Store at 2–8 °C, protected from light, under argon. Shipped on wet ice. Keep container tightly closed. Limit headspace oxygen and moisture ingress to preserve material quality.
• Incompatibilities (general): strong bases or prolonged basic aqueous conditions will deprotect the MIDA and generate the free boronic acid; strong oxidants may degrade the vinyl group or the boronate. Avoid strong acids/bases during storage and processing unless intentional.
• PPE: laboratory coat, suitable gloves (e.g., nitrile), and safety glasses as minimum. Use a certified fume hood to avoid dust exposure and to handle solvents and catalytic systems used in cross-couplings.
• First aid overview: if on skin/eyes, rinse with water for several minutes; remove contaminated clothing. If inhaled, move to fresh air. If ingested, rinse mouth. Seek medical attention as appropriate. Defer to SDS for details.
• Fire safety: treat as an organic solid; use CO2, dry chemical, or foam. Combustion may produce CO/CO2 and boron-containing residues.

Solvent Selection

This product is a solid aryl MIDA boronate used as a coupling building block, not a solvent. Solvent selection pertains to its dissolution and reaction use.

• Polarity/miscibility (general behavior):
  • Readily handled in polar aprotic organic solvents used in cross-couplings: THF, 1,4-dioxane, DMF, DMAc, DMSO, MeCN, and CH2Cl2. Solubility in toluene/EtOAc varies by substitution.
  • Limited solubility in water under neutral conditions; increases under basic aqueous media upon MIDA hydrolysis.
• Typical solvent systems by application:
  • Suzuki–Miyaura coupling: dioxane/water or THF/water mixtures under base; also pure polar aprotic solvents with phase-transfer base.
  • In situ MIDA deprotection then coupling: aqueous NaOH or Na2CO3 in dioxane/H2O or MeOH/H2O, followed by cross-coupling in the same pot (literature practice).
  • Purification: normal-phase silica using CH2Cl2/EtOAc/MeOH gradients, or reverse-phase if needed for polar impurities.
• When to choose alternatives:
  • If poor dissolution limits rate, switch to higher-permittivity solvents (DMF/DMAc) or warm THF/dioxane.
  • For greener profiles, consider 2-MeTHF or CPME in place of THF/dioxane where compatible with base and catalyst systems (see Green Alternatives).

Always verify solvent compatibility with your Pd catalyst/ligand and base system.

Storage and Reconstitution

• Storage (Product Data): Store at 2–8 °C, protected from light, under argon. Shipments are on wet ice. Keep tightly sealed to limit moisture/oxygen ingress and preserve vinyl integrity.
• Stability: MIDA boronates are generally bench-stable solids; however, prolonged exposure to strong base or aqueous media will hydrolyze the MIDA, liberating the boronic acid. Avoid unnecessary freeze–thaw or temperature cycling.
• Reconstitution/handling:
  • Open under inert gas if possible. Allow the vial to equilibrate to room temperature before opening to minimize condensation.
  • Dissolve in a suitable dry organic solvent (e.g., THF, dioxane, DMF, DMSO, MeCN, CH2Cl2) for reaction charging. Sonication or gentle warming may aid dissolution.
  • For in situ deprotection, add the solid or a stock solution to an aqueous base/organic mixture as specified by your coupling protocol.
• Packaging: If transferring to working vials, purge with argon or nitrogen and protect from ambient light.

Always refer to the item’s CoA/SDS for any additional storage precautions or stability notes specific to the supplied batch.

Structure and Identity

4-vinylphenylboronate MIDA ester is the N-methyliminodiacetate (MIDA) cyclic boronate of 4-vinylphenylboronic acid, designed as a bench-stable, masked boronic acid for cross-coupling chemistry.

• Item-specific identifiers (from Product Data):

  • CAS: 1422172-82-4
  • CID: 162422665
  • InChIKey: 20181 (as provided; atypical length—refer to CoA/SDS for confirmation)
  • SMILES: Not specified for this item; refer to CoA/Spec Sheet.
  • Molecular formula: Not specified for this item; refer to CoA/Spec Sheet.
  • Molecular weight: Not specified for this item; refer to CoA/Spec Sheet.

• Structural features (general/literature description):

  • Composed of a para-vinyl phenyl ring (styrenyl fragment) bonded to boron.
  • Boron is incorporated into a five-membered MIDA boronate ring formed by chelation with N-methyliminodiacetic acid (a diacid imide), yielding a neutral, cyclic boronate ester.
  • Functional groups: aryl–B(MIDA), vinyl (terminal alkene), tertiary amide within the MIDA scaffold, and two ester-like B–O linkages in the chelate.
  • 2D description: a para-vinyl substituent on a phenyl ring; at the ipso carbon opposite the vinyl group, a B center is chelated by a –N(Me)–CH2–CO–O– and –O–CO–CH2–N(Me) bidentate fragment, forming the canonical MIDA ring.

• Stereochemistry: none (achiral), unless downstream transformations introduce chirality.

Note: Exact identifiers (SMILES/InChI) for this catalog item should be taken from the official CoA/SDS if required for registration or inventory systems.

Synthetic Utility

Functional elements and their reactivity (general/literature):

• Aryl–B(MIDA): MIDA masking imparts air/moisture stability, enabling staged Suzuki–Miyaura couplings. Under base, controlled hydrolysis yields the active boronic acid or boronate, compatible with diverse electrophiles (Ar–X, vinyl–X, where X = Br, I, OTf).
• Para-vinyl group: orthogonal handle for olefin chemistry—Heck coupling, hydroboration–oxidation (to benzylic alcohols), epoxidation, dihydroxylation, cross-metathesis, hydrosilylation, or radical additions. Protecting-group-like orthogonality enables two-directional growth.
• Retrosynthetic value: Decouples installation of the aryl unit (via coupling) from subsequent vinyl functionalization; MIDA protection allows iterative coupling strategies without premature protodeboronation or transesterification.

Tactical highlights:

• Iterative cross-coupling: Use MIDA boronate as a latent nucleophile; perform electrophile-side coupling first if needed, then deprotect for the next coupling step.
• Chemoselectivity: Tune base strength and water content to control rate of MIDA hydrolysis vs cross-coupling turnover; additives (e.g., KF) can accelerate transmetalation with certain catalysts.
• Purification: MIDA boronates often crystallize well; silica chromatography is feasible. Avoid prolonged basic silica to prevent hydrolysis.

This combination of a stable boron masking group and a reactive vinyl handle makes the reagent particularly versatile for modular synthesis.

Target Specificity

Not applicable. This product is a small-molecule synthetic building block, not a biological macromolecule or affinity reagent. No antigen/epitope or species reactivity data are relevant.