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[ CAS No. 4406-72-8 ] {[proInfo.proName]}

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Chemical Structure| 4406-72-8
Chemical Structure| 4406-72-8
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Product Details of [ 4406-72-8 ]

CAS No. :4406-72-8 MDL No. :
Formula : C8H9BO2 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 147.97 Pubchem ID :-
Synonyms :

Safety of [ 4406-72-8 ]

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Application In Synthesis of [ 4406-72-8 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 4406-72-8 ]

[ 4406-72-8 ] Synthesis Path-Downstream   1~20

  • 1
  • [ 4406-72-8 ]
  • [ 1138-52-9 ]
  • [ 62787-21-7 ]
  • 2
  • [ 4406-72-8 ]
  • [ 10045-45-1 ]
  • 1-ethyl-3-phenyl-1,3-dihydro-2H-benzo[d]imidazol-2-one [ No CAS ]
  • 3
  • hexanoic acid 2-pyridinylmethyl ester [ No CAS ]
  • [ 4406-72-8 ]
  • [ 942-92-7 ]
YieldReaction ConditionsOperation in experiment
72% With dodecacarbonyl-triangulo-triruthenium In toluene at 140℃; for 20h;
  • 4
  • (4-chloro-phenyl)-acetic acid pyridin-2-ylmethyl ester [ No CAS ]
  • [ 4406-72-8 ]
  • [ 6332-83-8 ]
  • 5
  • [ 4406-72-8 ]
  • [ 62961-64-2 ]
  • (+)-diisopropyl tartrate phenylboronic ester [ No CAS ]
  • 6
  • [ 4406-72-8 ]
  • [ 2160-93-2 ]
  • [ 73029-08-0 ]
YieldReaction ConditionsOperation in experiment
0% In chloroform-d1 inder inert atm., at 25°C, for 72 h, in NMR tube; monitoring by (1)H NMR;
  • 7
  • [ 100-42-5 ]
  • [ 4406-72-8 ]
  • [ 612-00-0 ]
YieldReaction ConditionsOperation in experiment
91% With potassium <i>tert</i>-butylate; oxygen; (-)-sparteine In isopropyl alcohol at 55℃; for 24h;
91% With potassium <i>tert</i>-butylate; oxygen; isopropyl alcohol at 55℃; for 24h; 4.2 Diaryl methane units are prevalent in biologically active small molecules and this method can allow the rapid highly regioselective synthesis of this functionality. To explore the scope of the reductive coupling of boronic esters and styrenes, the above conditions were used to synthesize a variety of diaryl methane-containing products (Table 6). All of the reductive coupling reactions are highly regioselective (>25:1), and the reactions of simple coupling partners give high yields (78-91%) of isolated diaryl methane-containing products (Table 6, entries 1-3). The results demonstrate that substrates containing acid-sensitive functional groups are stable to the reductive coupling reaction conditions; for example, acetal protecting groups, which are readily removed upon work up, are compatible with the reaction conditions (Table 6, entries 5-7). Arylboronic esters containing electron-donating groups react more slowly, thereby requiring a higher catalyst loading (Table 6, entries 8 and 9), and ortho substitution on the arylboronic acid is tolerated (Table 6, entry 10). The ester functionality is also compatible, however an increase in [sp] is required to achieve a 63% yield of 3k (Table 6, entry 11). On the basis of our previous mechanistic hypothesis that the formation of a ϖ-benzyl intermediate is responsible for the outstanding regioselectivity, a diene substrate, which can form a similar ϖ-allyl species, was evaluated and yielded the reductive coupling product 31 in 41% yield as a greater than 25:1 mixture of regioisomers (Table 6, entry 12). Under these conditions both vinylboronic esters and simple alkenes, which rapidly isomerize, do not undergo an effective reductive coupling reaction. Even though a chiral additive (sp) is used, less than 5% enantiomer excess (ee) is observed for the product.After exploring the scope, there were three mechanistic questions to address: 1) what is the efficiency of alcohol oxidation as compared to product formation? 2) why are three equivalents of the arylboronic ester required for good product yields? and 3) why is exogenous sp required for catalysis? To investigate the first question, a higher molecular weight alcohol, sec-BuOH, was used as the solvent in order to use GC analysis to effectively measure the amount of ketone being formed via alcohol oxidation. A time course analysis of the reaction was performed and the GC yields of the hydroarylation product 3a and butan-2-one (5) as well as the percent styrene 1a remaining were plotted as a function of time (FIG. 4a). Initially, the yield of 3a and 5 are equivalent until 60% conversion, which is consistent with the oxidation of one alcohol directly yielding product. This also suggests that the PdII-hydride formed via alcohol oxidation reacts with the alkene faster than it reductively eliminates. In contrast, as the reaction progresses to higher substrate conversion, the yield of the 5 increases at a rate different than that of product formation. This shows as the concentration of alkene decreases, the PdII-hydride can undergo other competitive reactions including reductive elimination. The GC yield of 3a was 78% in sec-BuOH as compared to 91% in IPA indicating a modest solvent dependence.The next question investigated was, why are three equivalents of 2a required? Therefore, the fate of the boronic ester was investigated as the reaction progressed (FIG. 4b). Over an equivalent of 2a was consumed at 30 minutes after which a relatively linear decrease in concentration was observed (the scatter can be attributed to hydrolysis of 2a on silica before GC analysis). Besides the hydroarylation product 3a, two major byproducts, biphenyl (6) and phenol (7), derived from the boronic ester were observed. A 10% GC yield of biphenyl, the product of oxidative boronic acid homocoupling, is formed at 2 h, but a 14% yield of biphenyl (0.28 equiv. of 2a consumed) is observed overall. Phenol is the major byproduct of this reaction and is formed consistently throughout the reaction (1.3 equiv. of 2a). Phenol is likely formed from the reaction of the boronic ester with H2O2 formed from the reduction of O2 during catalyst regeneration. Together these data account for the undesired pathways that consume the excess arylboronic ester required.The final mechanistic question was the role(s) of sp considering that performing the reaction without exogenous sp leads to poor catalysis. Several functions of sp can be envisioned including acting as a ligand to stabilize Pd0 during catalyst regeneration, acting as a ligand on PdII during the reductive coupling process, and/or to break up the dimeric [Pd(SiPr)Cl2]2 complex. The first two roles are difficult to directly probe, however an experiment was performed to investigate the feasibility of sp breaking up the dimer complex. The experiment involved dissolving [Pd(SiPr)Cl2]2 and 2 equiv. of sp in 1,2-dichloroethane (DCE). The resulting mixture was heated to reflux for 2 h (FIG. 5). An aliquot of the mixture was analyzed by ESI-MS. Excitingly, the major Pd-complex observed in solution corresponds to Pd(SiPr)(sp)Cl2 [m/z (MH+)+=801.3]. Based upon the trans-geometry of related Pd(NHC)(pyridine)Cl2 complexes, the formation of complex 8 in which the NHC ligand is trans to the monodendate sp ligand is a proposed mechanism. Unfortunately, attempts to isolate complex 8 only led to the [Pd(SiPr)Cl2]2 complex and free sp. This shows that complex 8 is in equilibrium with the dimer. It should be noted that Pd[(-)-sparteine]Cl2 is not observed by ESI-MS. Interestingly, other simple amine bases do not lead to an effective catalytic system for reductive coupling. Possible explanations for this are the large size of sp facilitates ligand dissociation or the free nitrogen of sp could act as an intramolecular base.
91% With di-μ-chlorobis[chloro(N,N'-bis-(2,6-(diisopropyl)phenyl)imidazolidine-2-ylidene)palladium]; potassium <i>tert</i>-butylate; oxygen; isopropyl alcohol; (-)-sparteine at 55℃; for 24h; regioselective reaction;
  • 8
  • [ 4406-72-8 ]
  • [ 108-95-2 ]
YieldReaction ConditionsOperation in experiment
92% With sodium chlorite In water at 20℃; for 0.75h;
90% With copper ferrite; oxygen In water at 27℃; for 0.75h;
87% With C18H28Cl2CuN2O4 In water at 26℃; for 0.5h; 2.5 General procedure for synthesis of phenols by CuCl2-cryptand [2.2.Benzo] catalyst General procedure: For ipso-hydroxylation of aryl/heretoaryboronic acids and esters (Scheme 1), 1mmol aryl or heteroaryl boronic acid and esters in 2ml distilled water was taken in a 50ml RB and 5mol% of complex C1 was added. The mixture was stirred at room temperature for 20min. After completion of the reaction (as monitored by TLC), the reaction mixture was centrifuged to separate the catalyst and reused in further reactions. The product obtained was extracted with diethyl ether from the reaction mixture for two to three times. All the synthesised products of phenols were purified by column chromatography and characterized by GC-MS, FT-IR, 1H and 13C NMR spectroscopy.
86% With dihydrogen peroxide In water at 20℃; for 0.0833333h;
82% With 1,10-Phenanthroline; copper(II) sulfate; potassium hydroxide In water at 20℃; for 10h;
82% With water; dihydrogen peroxide; boric acid In ethanol at 20℃; for 1h; Green chemistry;
81% With N,N-dimethyl-p-toluidine N-oxide In dichloromethane at 20℃; for 1h;
73% With 1-carboxymethyl-3-methylimidazolium tetrachloroferrate; dihydrogen peroxide In neat (no solvent) at 20℃; for 1h;
61% With [bis(acetoxy)iodo]benzene; water; triethylamine In acetonitrile at 20℃; for 1h; General procedure for syntheses of aromatic alcohols General procedure: To a stirred solution of appropriate organoboronic acids (0.5 mmol, 1.0 equiv.) and Et3N(1.0 mmol, 2.0 equiv.) in CH3CN(acetonitrile: 3 mL, H2O: 11µL, 0.6mmol, 1.2 equiv.), DAIB (0.75 mmol, 1.5 equiv.), dissolved in acetonitrile (2mL) was added drop wise at room temperature and the mixture was allowed to stir for 10 minutes at that temperature. After completion of the reaction indicated by TLC, the reaction mixture was washed with distilled water (3×7 mL) and extracted with CH2Cl2(3×10 mL). The combined organic phase was dried over Na2SO4 and after evaporating the solvent, the residue was purified by column chromatography over silica gel using hexane/EtOAc as eluent to provide the pure target product.
61% With sodium periodate; iodobenzene In water; acetonitrile at 80℃; for 8h; General procedure for syntheses of aromatic alcohols General procedure: Toa stirred solution of appropriate organoboronic acids (1.0 mmol, 1.0 equiv.)and NaIO4 (2.0 mmol, 2.0 equiv.) in CH3CN-H2O (acetonitrile: 6 mL, H2O: 2 mL), iodobenzene (0.1 mmol, 10 mol%) was added and the mixture was heated at 80 0C for 8 h. The mixture was cooled and concentrated under vacuum. It was then washed with distilled water (3×4 mL) and extracted with CH2Cl2 (3×7 mL). The combinedorganic phase was dried over Na2SO4 and after evaporating the solvent, the residue was purified by column chromatography over silica gelusing hexanes/EtOAc as eluent to provide the pure target product.

  • 9
  • [ 4406-72-8 ]
  • [ 2442-10-6 ]
  • [ 181036-39-5 ]
YieldReaction ConditionsOperation in experiment
95% With Pd(IiPr)(OTs)2; oxygen; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 24h;
77% With oxygen; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h; regioselective reaction;
65% With oxygen; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h;
55% With oxygen; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h; regioselective reaction;
43% With oxygen; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 72h; regioselective reaction;

  • 10
  • [ 10075-50-0 ]
  • [ 4406-72-8 ]
  • [ 66616-72-6 ]
YieldReaction ConditionsOperation in experiment
84% With tris [tris(3,5-bis(trifluoromethyl)phenyl)phosphine]palladium(0); potassium carbonate In methanol; water at 110℃; for 1h;
  • 11
  • [ 4406-72-8 ]
  • [ 1968-40-7 ]
  • (E)-ethyl 5-phenylpent-4-enoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% With oxygen; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h; regioselective reaction;
69% With oxygen; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h; regioselective reaction;
61% With oxygen; palladium diacetate; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h;
  • 12
  • [ 53710-18-2 ]
  • [ 4406-72-8 ]
  • [ 92-07-9 ]
  • 13
  • [ 53710-18-2 ]
  • [ 4406-72-8 ]
  • [ 92-07-9 ]
  • [ 92-52-4 ]
  • 14
  • [ 53710-18-2 ]
  • [ 4406-72-8 ]
  • [ 92-52-4 ]
  • 15
  • [ 4406-72-8 ]
  • [ 31462-58-5 ]
  • [ 34771-45-4 ]
  • 16
  • [ 4406-72-8 ]
  • [ 182275-70-3 ]
  • [ 35070-08-7 ]
  • 17
  • [ 4406-72-8 ]
  • [ 626-00-6 ]
  • [ 92-06-8 ]
YieldReaction ConditionsOperation in experiment
24 mg With potassium phosphate; copper dichloride In N,N-dimethyl-formamide at 110℃; for 48h; Inert atmosphere;
  • 18
  • [ 625-92-3 ]
  • [ 4406-72-8 ]
  • [ 92-07-9 ]
  • [ 92-52-4 ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate; copper dichloride In N,N-dimethyl-formamide at 80℃; for 24h; Inert atmosphere;
  • 19
  • [ 4406-72-8 ]
  • [ 63721-05-1 ]
  • (E)-5-phenyl-3,3-dimethylpent-4-enoic acid methyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With oxygen; copper(II) bis(trifluoromethanesulfonate) In N,N-dimethyl acetamide at 40℃; for 48h; regioselective reaction;
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