235090-36-5

Upstream product

• 1663-39-4 tert-Butyl acrylate 
• 552-16-9 ortho-nitrobenzoic acid 
• 602-94-8 Pentafluorobenzoic acid 
• 118-91-2 ortho-chlorobenzoic acid 

Downstream Products

• 872526-10-8 t-butyl 2-hydroxy-3-(4-methylphenoxy)propioate 
• 872526-13-1 t-butyl 2-hydroxy-3-(4-trifluoromethylphenoxy)propioate 
• 872526-12-0 t-butyl 3-(4-bromophenoxy)-2-hydroxypropioate 
• 872526-11-9 t-butyl 2-hydroxy-3-(4-methoxyphenoxy)propioate 
• 872526-14-2 t-butyl 3-(3,5-dimethylphenoxy)-2-hydroxypropioate 
• 872526-09-5 t-butyl 2-hydroxy-3-phenoxypropioate 
• 872526-19-7 t-butyl (4-trifluoromethylphenoxy)pyruvate 
• 872526-20-0 t-butyl (3,5-dimethylphenoxy)pyruvate 
• 872526-18-6 t-butyl (4-bromophenoxy)pyruvate 
• 872526-17-5 t-butyl (4-methoxyphenoxy)pyruvate 
• 872526-16-4 t-butyl (4-methylphenoxy)pyruvate 
• 872526-15-3 t-butyl phenoxypyruvate 

Relevant academic research and scientific papers

Cis-Dihydroxylation of electron deficient olefins catalysed by an oxo-bridged diiron(III) complex with H2O2

Room temperature oxidation of olefins catalysed by a symmetrical (μ-oxo)(μ-hydroxo)diiron(III) complex (1) based on the amino pyridyl ligand bpmen (bpmen = N,N′-dimethyl-N,N′-bis(2-pyridyl methyl)ethane-1,2-diamine) with hydrogen peroxide under the conditions of limiting substrate is described. Excellent substrate conversions have been achieved under ambient reaction conditions. The olefin oxidation efficacy of the 1/H2O2 system has been found to get improved in presence of acetic acid. The catalytic system has been shown to oxidise electron-deficient olefins to the corresponding cis-diols, while epoxidation is favoured in case of electron-rich olefins. The μ-oxo diiron(III) core of the catalyst 1 has been found be regenerated after the catalytic turnovers. Addition of a second batch of substrate and oxidant at the end of the olefin oxidation results in the formation of almost identical amounts of epoxides/diols. Moreover, the regenerated catalyst exhibits a significantly higher preference towards the oxidation of electron-deficient olefins.

Iron catalyzed competitive olefin oxidation and ipso-hydroxylation of benzoic acids: Further evidence for an FeV=O oxidant

The iron complex [FeII(TPA)(CH3CN) 2](OTf)2 (1) [TPA = tris(2-pyridylmethyl)amine] with H2O2 as an oxidant performs ipso-hydroxylation of electron-withdrawing benzoic acids at room temperature, leading to multiple turnovers of corresponding phenols. ipso-Hydroxylation competes with olefin epoxidation and cis-dihydroxylation in the presence of olefins, with the product ratios being modulated by the relative amounts of benzoic acid, olefin, and water. It is proposed that benzoic acid and water compete for the available sixth site on the [(TPA)FeIII(OOH)] intermediate, which undergoes O-O bond heterolysis to form, respectively, the FeV(O)(O2CAr) and FeV(O)(OH) oxidants that determine the product outcome. The putative FeV(O)(O2CAr) oxidant decays either by undergoing oxidative decarboxylation and subsequent ipso-hydroxylation to form the observed phenol product or by oxo-transfer to olefins to form epoxide. The observed higher yield of phenol over epoxide or cis-diol in all cases studied, where an electronwithdrawing benzoic acid is present in the reaction mixture, suggests that intramolecular decay of the putative FeV(O)-(O 2CAr) oxidant is favored over intermolecular olefin oxidation. These results support the mechanistic framework postulated for Fe(TPA) oxidative catalysis and further strengthens the notion that oxoiron(V) species are the key oxidants in these reactions.

Iron-catalyzed asymmetric olefin cis-dihydroxylation with 97% enantiomeric excess

Big cis-ster: The use of an (R,R)-bipyrrolidine backbone with two α-methylpyridine pendant arms affords a tetradentate N4 ligand that coordinates an iron center with cis-α topology (see picture; Fe purple, C gray, N blue, O red, S yellow, F green). This complex catalyzes the reaction between H2O2 and cis-2-heptene to afford a cis-diol product in very high enantioselectivity. (Figure Presented)

Iron-catalyzed olefin epoxidation in the presence of acetic acid: Insights into the nature of the metal-based oxidant

The iron complexes [(BPMEN)Fe(OTf)2] (1) and [(TPA)Fe(OTf) 2] (2) [BPMEN = N,N′-bis-(2-pyridylmethyl)-N,N′-dimethyl- 1,2-ethylenediamine; TPA = tris-(2-pyridylmethyl)amine] catalyze the oxidation of olefins by H2O2 to yield epoxides and cis-diols. The addition of acetic acid inhibits olefin cis-dihydroxylation and enhances epoxidation for both 1 and 2. Reactions carried out at 0°C with 0.5 mol % catalyst and a 1:1.5 olefin/H2O2 ratio in a 1:2 CH 3CN/CH3COOH solvent mixture result in nearly quantitative conversions of cyclooctene to epoxide within 1 min. The nature of the active species formed in the presence of acetic acid has been probed at low temperature. For 2, in the absence of substrate, [(TPA)FeIII(OOH) (CH3COOH)]2+ and [(TPA)FeIVO(NCCH 3)]2+ intermediates can be observed. However, neither is the active epoxidizing species. In fact, [(TPA)FeIVO(NCCH 3)]2+ is shown to form in competition with substrate oxidation. Consequently, it is proposed that epoxidation is mediated by [(TPA)FeV(O)(OOCCH3)]2+, generated from O-O bond heterolysis of the [(TPA)FeIII(OOH)(CH3COOH)] 2+ intermediate, which is promoted by the protonation of the terminal oxygen atom of the hydroperoxide by the coordinated carboxylic acid.