4250-47-9

Upstream product

• 108-88-3 toluene 
• 7446-70-0 aluminium trichloride 
• 10294-34-5 boron trichloride 
• 74-88-4 methyl iodide 
• 19287-45-7 diborane 
• 5955-19-1 3-methylphenylmercuric chloride 
• 7294-50-0 tri-o-tolylboroxine 
• 106-42-3 para-xylene 
• 35569-54-1 Tri-m-tolyl-stibane 
• 21022-98-0 (2,5-dimethylphenyl)dichloroborane 
• 2777-37-9 2-methylphenylmercuric chloride 

Downstream Products

• 96487-03-5 2-(3-methylphenyl)-benzo-1,3-dioxo-borole 
• 223799-24-4 2-(3-methyl-phenyl)-5,5-dimethyl-[1,3,2]dioxaborinane 
• 17806-43-8 3-C₆H₄-3'-COOH-1.2-C₂B₁₀H₁₁ 
• 42568-54-7 2-C₆H₄-3'-COOH-1.7-C₂B₁₀H₁₁ 
• 17806-47-2 3-(C₆H₄-3-CH₃)-o-HCB₁₀H₉CH 
• 42568-53-6 2-(C₆H₄-3-CH₃)-1.7-C₂B₁₀H₁₁ 
• 98221-23-9 2-(3-methylphenyl)-naphtho{2,3-d}-1,3-dioxo-borole 
• 108-39-4 3-methyl-phenol 

Relevant academic research and scientific papers

Synthesis of arylboronates by boron-induced ipso-deantimonation of triarylstibanes with boron trihalides and its application in one-pot two-step transmetallation/cross-coupling reactions

The reaction of triarylstibanes (1) with boron trihalides (BCl3, and BBr3) afforded arylboron dihalides (2) by utilizing all the three aryl groups on the antimony. Boron intermediates (2) were transformed to arylboronates (3) in good to excellent yields by treatment with methanol and 1,3-propanediol. Further, the Pd-catalyzed reactions of 2 with organic halides such as 1-bromonaphthalene and benzoyl chloride in the presence of H2O afforded the corresponding cross-coupling products, unsymmetrical biaryls (4) and ketones (5), in moderate to good yields. The potential energy surfaces for the transmetallations of triarylstibanes (1) with BCl3 affording 2 were determined by molecular orbital calculations. The analyses of substituent effects on theoretically calculated reactivities showed the importance of the resonance effects of the ring substituents on these transmetallations.

Mechanistic studies into amine-mediated electrophilic arene borylation and its application in MIDA boronate synthesis

Direct electrophilic borylation using Y2BCl (Y2 = Cl2 or o-catecholato) with equimolar AlCl3 and a tertiary amine has been applied to a wide range of arenes and heteroarenes. In situ functionalization of the ArBCl2 products is possible with TMS 2MIDA, to afford bench-stable and easily isolable MIDA-boronates in moderate to good yields. According to a combined experimental and computational study, the borylation of activated arenes at 20 C proceeds through an S EAr mechanism with borenium cations, [Y2B(amine)] +, the key electrophiles. For catecholato-borocations, two amine dependent reaction pathways were identified: (i) With [CatB(NEt 3)]+, an additional base is necessary to accomplish rapid borylation by deprotonation of the borylated arenium cation (σ complex), which otherwise would rather decompose to the starting materials than liberate the free amine to effect deprotonation. Apart from amines, the additional base may also be the arene itself when it is sufficiently basic (e.g., N-Me-indole). (ii) When the amine component of the borocation is less nucleophilic (e.g., 2,6-lutidine), no additional base is required due to more facile amine dissociation from the boron center in the borylated arenium cation intermediate. Borenium cations do not borylate poorly activated arenes (e.g., toluene) even at high temperatures; instead, the key electrophile in this case involves the product from interaction of AlCl3 with Y2BCl. When an extremely bulky amine is used, borylation again does not proceed via a borenium cation; instead, a number of mechanisms are feasible including via a boron electrophile generated by coordination of AlCl3 to Y2BCl, or by initial (heteroarene)AlCl3 adduct formation followed by deprotonation and transmetalation.

A New Borylation Method for Alkylbenzene and Polystyrene

The borylation of alkylbenzenes by Hal2BH (Hal = F, Cl, Br) gives H2 and a mixture of m- and p-alkyl(dihaloboryl)benzenes.In the case of bulky alkyl groups, such as isopropyl, tert-butyl, these are partially split off as R - H and RBHal2.The phenyl groups in polystyrene-divinylbenzene copolymers undergo borylation with Br2BH in a 55percent yield.

Methyl group migration in the preparation of o-tolyl- and p-xylyldichloroboranes

In the preparation of o-tolyldichloroborane and p-xylyldichloroborane migration of the methyl group ortho to the BCl2 group occurred. The evidence suggests that rearrangement occurs in a transition state in which the BCl2 group is only weakly bonded to the aromatic system.