Iodotrimethylsilane

Jung, Michael E.; Martinelli, Michael J.; Oláh, George A.; Prakash, G. K. Surya; Hu, Jinbo

doi:10.1002/047084289x.ri043.pub2

Cited by 4 publications

(4 citation statements)

References 148 publications

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“…Nevertheless, the use of a mixture of chlorotrimethylsilane with NaI in acetonitrile can be used to achieve the silylation of dialkyl phosphonates that can be then transformed in phosphonic acids after hydrolysis or methanolysis. Following these experimental conditions, the efficacy is likely explained by the in situ generation of iodotrimethylsilane that result from a halogen exchange reaction [ 169 ]. This method (ClSiMe 3 + NaI in acetonitrile) is currently less employed likely due to the need to remove NaI from the final phosphonic acid after the step of hydrolysis or methanolysis.…”

Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

149

103

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The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

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Section: Reviewmentioning

confidence: 99%

Phosphonic acid: preparation and applications

Sevrain¹,

Berchel²,

Couthon³

et al. 2017

Beilstein J. Org. Chem.

149

103

View full text Add to dashboard Cite

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“…They are readily miscible with nonpolar alkane and arene solvents such as hexane and toluene. These electrophilic reagents are known for their reactivity with a wide range of nucleophiles; typical reactions involve substitution of the halide for a nucleophile resulting in a stronger Si-nucleophile bond, e.g., to generate Si–O or Si–N bonds. − The Si–X bond strength decreases significantly from the lighter to the heavier halides, with TMS–X bond dissociation energies of 113, 96, and 77 kcal/mol for X = Cl, Br, and I, respectively . These numbers suggest that reactions involving substitution of, e.g., a Si–Cl bond for a Si–Br bond or a Si–Br bond for a Si–I bond, are likely to be favorable.…”

mentioning

confidence: 99%

Anion Exchange in Cesium Lead Halide Perovskite Nanocrystals and Thin Films Using Trimethylsilyl Halide Reagents

et al. 2018

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“…For example, bismuth can transfer a chlorine atom to 2-methyl- and 2,5-dimethyltetrahydrofurans, where the ring is preactivated with an acyl chloride (Figure a). , Numerous other acylative metal-catalyzed ring-opening reactions are known that rely on relieving ring strain, giving esters rather than completely deoxygenated products. , Tungsten hexachloride has been used to stoichiometrically cleave many ethers, including benzyl ether, to form alkyl chlorides (Figure d); a variety of other products including alcohols and overhalogenated compounds are invariably produced as well . Simple halogenating reagents such as trimethylsilyl iodide or concentrated hydrobromic or hydroiodic acid are generally effective (Figure b and c), but these aggressive reagents are typically required in excess and can form a variety of different products depending on the conditions used. ,, …”

Section: Introductionmentioning

confidence: 99%

α-Diimine-Niobium Complex-Catalyzed Deoxychlorination of Benzyl Ethers with Silicon Tetrachloride

et al. 2019

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α-Diimine niobium complexes serve as catalysts for deoxygenation of benzyl ethers by silicon tetrachloride (SiCl 4 ) to cleanly give two equivalents of the corresponding benzyl chlorides, where SiCl 4 has the dual function of oxygen scavenger and chloride source with the formation of a silyl ether or silica as the only byproduct. The reaction mechanism has two successive transetherification steps that are mediated by the niobium catalyst, first forming one equivalent of benzyl chloride along with the corresponding silyl ether intermediate that undergoes the same reaction pathway to give the second equivalent of benzyl chloride and silyl ether.

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Iodotrimethylsilane

Cited by 4 publications

References 148 publications

Phosphonic acid: preparation and applications

Phosphonic acid: preparation and applications

Anion Exchange in Cesium Lead Halide Perovskite Nanocrystals and Thin Films Using Trimethylsilyl Halide Reagents

α-Diimine-Niobium Complex-Catalyzed Deoxychlorination of Benzyl Ethers with Silicon Tetrachloride

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