5205-04-9

Usage

Primary Uses

Solvent
Intermediate in the production of other chemicals

Common Applications

Plasticizer
Additive in the production of resins, coatings, and adhesives

Pharmaceutical Industry Use

Carrier or solvent for drugs

Safety Considerations

Relatively safe when used in approved applications
Prolonged or excessive exposure may cause irritation to eyes, skin, and respiratory system
Toxic effects if ingested in large quantities

Handling and Usage

Should be handled and used with care due to potential health risks

Upstream product

• 2568-33-4 3-methyl-butane-1,3-diol 
• 98-88-4 benzoyl chloride 
• 542-91-6 H₂SiEt₂ 
• 5205-11-8 3-methyl-2-butenyl benzoate 
• 58303-59-6 2-phenyl-4,4-dimethyl-1,3-dioxane 
• 93-97-0 benzoic acid anhydride 
• 10364-94-0 1-benzoylimidazole 
• 94-46-2 isoamyl benzoate 
• 617-86-7 triethylsilane 
• 5205-12-9 3-methylbut-3-enyl benzoate 
• 775-12-2 diphenylsilane 
• 694-53-1 phenylsilane 
• 524-38-9 N-hydroxyphthalimide 
• 776-76-1 methyldiphenylsilane 

Relevant academic research and scientific papers

Bis(pentafluorophenyl) disulfide as a hydrogen abstractor and an electron acceptor from the resulting radical intermediate

The pentafluorobenzenethiyl radical is an efficient hydrogen abstractor from an activated methylene or methine group and bis(pentafluorophenyl) disulfide is an efficient electron acceptor from the resulting radical intermediate. Thus benzyl-OTBS ether was easily converted into the corresponding pinacol, and 2-phenyl-1,3-dioxanes are converted into the monobenzoates of diols.

Fe-Catalyzed Anaerobic Mukaiyama-Type Hydration of Alkenes using Nitroarenes

Hydration of alkenes using first row transition metals (Fe, Co, Mn) under oxygen atmosphere (Mukaiyama-type hydration) is highly practical for alkene functionalization in complex synthesis. Different hydration protocols have been developed, however, control of the stereoselectivity remains a challenge. Herein, highly diastereoselective Fe-catalyzed anaerobic Markovnikov-selective hydration of alkenes using nitroarenes as oxygenation reagents is reported. The nitro moiety is not well explored in radical chemistry and nitroarenes are known to suppress free radical processes. Our findings show the potential of cheap nitroarenes as oxygen donors in radical transformations. Secondary and tertiary alcohols were prepared with excellent Markovnikov-selectivity. The method features large functional group tolerance and is also applicable for late-stage chemical functionalization. The anaerobic protocol outperforms existing hydration methodology in terms of reaction efficiency and selectivity.

Erratum: Ruthenium-catalyzed C-H hydroxylation in aqueous acid enables selective functionalization of amine derivatives (Journal of the American Chemical Society (2017) 139:28 (9503-9506) DOI: 10.1021/jacs.7b05469)

Page 9504. The structure of product 3cc in Table 2 was found to be mis-assigned. We thank Prof. Phil Baran and Dr. Rafael Navratil for bringing this error to our attention. The correct structure contains an additional benzylic alcohol at the C-9 position of the steroid (3cc′, shown below). With the accompanying change in molecular weight, the isolated yield is 29%. Supporting Information. The incorrect structure and yield also appeared on pages S20 and S84 in the SI. Given this, the HRMS entry on page S20 should read as follows: “HRMS (ESI-TOF) m/z calcd for C19H18F3O5S+ (M-O+Na)+ 415.0822, found 415.0857”. The complete corrected SI is provided here.

Iron-Catalyzed Reductive Vinylation of Tertiary Alkyl Oxalates with Activated Vinyl Halides

We present herein a rare and efficient method for the creation of vinylated all carbon quaternary centers via Fe-catalyzed cross-electrophile coupling of vinyl halides with tertiary alkyl methyl oxalates. The reaction displays excellent functional group tolerance and broad substrate scope, which allows cascade radical cyclization and vinylation to afford complex bicyclic and spiral structural motifs. The reaction proceeds via tertiary alkyl radicals, and the putative vinyl-Br/Fe complexation appears to be crucial for activating the alkene and enabling a possibly concerted radical addition/C-Fe forming process.

Dehydroxylative Fluorination of Tertiary Alcohols

A large number of fluorination methods have been developed, but the construction of a tertiary C-F bond remains challenging. Herein, we describe an efficient dehydroxylative fluorination of tertiary alcohols with Selectfluor via the activation of a hydroxyl group by a Ph2PCH2CH2PPh2/ICH2CH2I system. Although the reagents appear to be not compatible (Selectfluor with the phosphine and I- generated in situ), the reactions occur rapidly to give the desired products in moderate to high yields. This work may present a new discovery in fluorination of alcohols since the reported methods are mainly limited to primary and secondary alcohols.

Direct Oxidation of Csp3?H bonds using in Situ Generated Trifluoromethylated Dioxirane in Flow

A fast, scalable, and safer Csp3?H oxidation of activated and un-activated aliphatic chains can be enabled by methyl(trifluoromethyl)dioxirane (TFDO). The continuous flow platform allows the in situ generation of TFDO gas and its rapid reactivity toward tertiary and benzylic Csp3?H bonds. The process exhibits a broad scope and good functional group compatibility (28 examples, 8–99 %). The scalability of this methodology is demonstrated on 2.5 g scale oxidation of adamantane.

Mechanistic Study of Ruthenium-Catalyzed C-H Hydroxylation Reveals an Unexpected Pathway for Catalyst Arrest

We have recently disclosed [(dtbpy)2RuCl2] as an effective precatalyst for chemoselective C-H hydroxylation of C(sp3)-H bonds and have noted a marked disparity in reaction performance between 4,4′-di-tert-butyl-2,2′-bipyridine (dtbpy)- and 2,2′-bipyridine (bpy)-derived complexes. A desire to understand the origin of this difference and to further advance this catalytic method has motivated the comprehensive mechanistic investigation described herein. Details of this reaction have been unveiled through evaluation of ligand structure-activity relationships, electrochemical and kinetic studies, and pressurized sample infusion high-resolution mass spectrometry (PSI-MS). Salient findings from this investigation include the identification of more than one active oxidant and three disparate mechanisms for catalyst decomposition/arrest. Catalyst efficiency, as measured by turnover number, has a strong inverse correlation with the rate and extent of ligand dissociation, which is dependent on the identity of bipyridyl 4,4′-substituent groups. Dissociated bipyridyl ligand is oxidized to mono- and bis-N-oxide species under the reaction conditions, the former of which is found to act as a potent catalyst poison, yielding a catalytically inactive tris-ligated [Ru(dtbpy)2(dtbpy N-oxide)]2+ complex. Insights gained through this work highlight the power of PSI-MS for studies of complex reaction processes and are guiding ongoing efforts to develop high-performance, next-generation catalyst systems for C-H hydroxylation.

C-H oxygenation at tertiary carbon centers using iodine oxidant

An oxidation system in which iodic acid (HIO3) is used as an oxidant in the presence of N-hydroxyphthalimide (NHPI) permitted the selective hydroxylation of tertiary C-H bonds and the lactonization of carboxylic acids containing a tertiary carbon center. These reactions are operationally simple and proceed under metal-free conditions using commercially available reagents, thus offering an ideal tool for the efficient oxidation of C-H bonds at tertiary carbon centers.

An inexpensive catalyst, Fe(acac)3, for regio/site-selective acylation of diols and carbohydrates containing a 1,2-: Cis -diol

This work describes the [Fe(acac)3] (acac = acetylacetonate)-catalyzed, regio/site-selective acylation of 1,2- and 1,3-diols and glycosides containing a cis-vicinal diol. The iron(iii) catalysts initially formed cyclic dioxolane-type intermediates with substrates between the iron(iii) species and vicinal diols, and the efficient and selective acylation of one hydroxyl group was subsequently achieved by adding acylation reagents in the presence of diisopropylethylamine (DIPEA) under mild conditions. This reaction generally produced high selectivities and highly isolated yields with the same protection pattern as that achieved with dibutyl tinoxide-mediated schemes.

Wacker-Type Oxidation Using an Iron Catalyst and Ambient Air: Application to Late-Stage Oxidation of Complex Molecules

A practical and general iron-catalyzed Wacker-type oxidation of olefins to ketones is presented, and it uses ambient air as the sole oxidant. The mild oxidation conditions enable exceptional functional-group tolerance, which has not been demonstrated for any other Wacker-type reaction to date. The inexpensive and nontoxic reagents [iron(II) chloride, polymethylhydrosiloxane, and air] can, therefore, also be employed to oxidize complex natural-product-derived and polyfunctionalized molecules.