19206-13-4

Upstream product

• 120-80-9 benzene-1,2-diol 
• 4250-48-0 (2-methylphenyl)dichloroborane 
• 127-18-4 1,1,2,2-tetrachloroethylene 
• 227310-43-2 [Os(CO)2(P(C₆H₅)3)2(C₆H₄CH₃)(BO₂C₆H₄)] 
• 13826-27-2 2,2'-bis(1,3,2-benzodioxaborole) 
• 274-07-7 benzo[1,3,2]dioxaborole 
• 108-88-3 toluene 
• 106-42-3 para-xylene 
• 118-90-1 ortho-methylbenzoic acid 
• 615-37-2 ortho-methylphenyl iodide 
• 16419-60-6 2-Methylphenylboronic acid 
• 133525-25-4 (2-CH₃-C₆H₄)B(O-i-C₄H₉)2 
• 2777-37-9 2-methylphenylmercuric chloride 

Downstream Products

• 195062-59-0 2-methylphenylboronic acid pinacol ester 

Relevant academic research and scientific papers

Reactions of B2(o-tolyl)4 with Boranes: Assembly of the Pentaborane(9), HB[B(o-tolyl)(μ-H)]4

Reactions of the diborane(4) B2(o-tolyl)4 and monohydridoboranes are shown to give B(o-tolyl)3 and (o-tolyl)BR2 (R2=(C8H14) 3, cat 4, pin 5, (C6F5)2/s

Activation of Aryl Carboxylic Acids by Diboron Reagents towards Nickel-Catalyzed Direct Decarbonylative Borylation

The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B2cat2 has been achieved without recourse to any additives. This Ni-catalyzed method exhibits a broad substrate scope covering poorly reactive non-ortho-substituted (hetero)aryl carboxylic acids, and tolerates diverse functional groups including some of the groups active to Ni0 catalysts. The key to achieve this decarbonylative borylation reaction is the choice of B2cat2 as a coupling partner that not only acts as a borylating reagent, but also chemoselectively activates aryl carboxylic acids towards oxidative addition of their C(acyl)?O bond to Ni0 catalyst via the formation of acyloxyboron compounds. A combination of experimental and computational studies reveals a detailed plausible mechanism for this reaction system, which involves a hitherto unknown concerted decarbonylation and reductive elimination step that generates the aryl boronic ester product. This mode of boron-promoted carboxylic acid activation is also applicable to other types of reactions.

Electronic Spectroscopy of 2-Phenyl-1,3,2-benzodioxaborole and Its Derivatives: Important Building Blocks of Covalent Organic Frameworks

Aryl boronate esters, such as 2-phenyl-1,3,2-benzodioxaborole (1), are important components in the formation of a variety of covalent organic frameworks. The addition of substituents on the aromatic rings of aryl boronate esters has the potential to modif

Metal-Free Radical Borylation of Alkyl and Aryl Iodides

A metal-free radical borylation of alkyl and aryl iodides with bis(catecholato)diboron (B2cat2) as the boron source under mild conditions is introduced. The borylation reaction is operationally easy to conduct and shows high functional group tolerance and broad substrate scope. Radical clock experiments and density functional theory calculations provide insights into the mechanism and rate constants for C-radical borylation with B2cat2 are disclosed.

Solid-state 11B and 13C NMR, IR, and X-ray crystallographic characterization of selected arylboronic acids and their catechol cyclic esters

Nine arylboronic acids, seven arylboronic catechol cyclic esters, and two trimeric arylboronic anhydrides (boroxines) are investigated using 11B solid-state NMR spectroscopy at three different magnetic field strengths (9.4, 11.7, and 21.1T). Through the analysis of spectra of static and magic-angle spinning samples, the 11B electric field gradient and chemical shift tensors are determined. The effects of relaxation anisotropy and nutation field strength on the 11B NMR line shapes are investigated. Infrared spectroscopy was also used to help identify peaks in the NMR spectra as being due to the anhydride form in some of the arylboronic acid samples. Seven new X-ray crystallographic structures are reported. Calculations of the 11B NMR parameters are performed using cluster model and periodic gauge-including projector-augmented wave (GIPAW) density functional theory (DFT) approaches, and the results are compared with the experimental values. Carbon-13 solid-state NMR experiments and spectral simulations are applied to determine the chemical shifts of the ipso carbons of the samples. One bond indirect 13C-11B spin-spin (J) coupling constants are also measured experimentally and compared with calculated values. The 11B/10B isotope effect on the 13C chemical shift of the ipso carbons of arylboronic acids and their catechol esters, as well as residual dipolar coupling, is discussed. Overall, this combined X-ray, NMR, IR, and computational study provides valuable new insights into the relationship between NMR parameters and the structure of boronic acids and esters. Copyright

Chelate restrained boron cations for intermolecular electrophilic arene borylation

Highly electrophilic boron species that borylate arenes are generated by halide abstraction from CatBX (Cat = catecholato, C6H 4O22-, X = Cl or Br) by [Et3Si] [CbBr6] (CbBr6 = [closo-1-H-CB11H 5Br6]-). A transient [CatB][CbBr6] related species reacts as a synthetic equivalent of [CatB]+ in intermolecular electrophilic borylation, with reactions proceeding rapidly at 25 °C. The [CatB]+ moiety was shown to be strongly Lewis acidic on the basis of 1H and 31P{1H} NMR spectroscopy of the crotonaldehyde and triethylphosphine oxide adducts, respectively. Catalytic quantities of [Et3Si][CbBr6] and CatBX were effective for the high-yielding borylation of arenes by CatBH in a highly atom efficient cycle with H2 the only byproduct. Successful catalysis was dependent on the robust [CbBr6]- anion and the use of electrophile-resistant borane sources

Reactions of cis and trans beat, aryl osmium complexes (cat == l,2-O2CeH4). Bis(bcat) complexes of osmium and ruthenium and a structural comparison ofcis and trans isomers of Os(Bcat)I(CO)2(PPh3)2

Reaction of Os(Bcat)Cl(CO)(PPh3)2 (1) (HBcat = catecholborane or 1,3,2-benzodioxaborole) with o-tolyllithium gives the yellow,; five-coordinate Beat, aryl complex Os(Bcat)(o-tolyl)(CO)(PPh3)2 (2). Treatment of 2 with carbon monoxide or p-tolylisocyanide gives the corresponding saturated Beat, aryl complexes cis-Os(Bcat)(o-tolyl)(CO)2(PPh3)2 (3) and c/sOs(Bcat)(o-tolyl)(CO)(CN-p-tolyl)(PPh3)2 (4). Complexes 3 and 4 decompose in benzene solution at room temperature to give o-tolylBcat and the orthometalated triphenylphosphine complexes Os(c5lJph2)H(CO)2(PPh3) (5) and Os(C6H4PPh2)H(CO)(CN-p-tolyl)(PPh3) (as a mixture of two isomers, 6a and 6b), respectively. In the presence of B2cat2, 3 and 4 react to give the bis(Bcat) complexes Os(Bcat)2(CO)2(PPh3)2 (7) and Os(Bcat)2(CO)(CN-p-tolyl)(PPh3)2 (8). Complex 3 also reacts with HBcat to produce Os(Bcat)H(CO)2(PPh3)2 (9). The bis(Bcat) ruthenium complexes Ru(Bcat)2(CO)2(PPh3)2 (10) and Ru(Bcat)2(CO)(CN-tolyl)(PPh3)2 (11) can be prepared by treatment of Ru(CO)2(PPh3)3 or Ru(CO)(CN-p-tolyl)(PPh3)3 with B2cat2. Complex 3 reacts with C12C=CC12 or CHC13 to produce OsCl(CCl=CCl2)(CO)2(PPh3)2 (12) or OsCl2(CO)2(PPh3)2, respectively. Complex 1 when treated with CO gives cis-Os(Bcat)Cl(CO)2(PPh3)2 (13), which in turn with phenyllithium or o-tolyllithium gives ￡rans-Os(Bcat)(Ph)(CO)2(PPh3)2 (14) orrans-Os(Bcat)(o-tolylXCO)2(PPh3)2 (15). Complex 15 reacts with I2 to give a mixture of ra7i$-Os(Bcat)I(CO)2(PPh3)2 (16) and rans-Os(o-tolyl)I(CO)2(PPh3)2 (17). Complex 16 is also formed by heating cts-Os(Bcat)I(CO)2(PPh3)2 (18) in benzene. Crystal structures of complexes, 5, 8,10, 11, 12, 16, and 18 are reported.