The Ozone—Hydrosilane Reaction: A Mechanistic Study

Spialter, Leonard; Pazdernik, L.; Bernstein, Stanley; Swansiger, W.A.; Buell, Glen R.; Freeburger, M. E.

doi:10.1021/ba-1972-0112.ch006

Cited by 13 publications

(3 citation statements)

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“…The kinetic isotope effect of k H / k D =1.15±0.15 for oxidation of 1 f and Et 3 SiD under the conditions in Table 2 is comparable to those of 1.23–1.40 for hydrolysis and alcoholysis of 1 f ,17b alkaline cleavage of triphenylsilane,31a and dichlorocarbene insertion into tri‐ n ‐butylsilane 31b. Kinetic studies on the catalytic oxidation of 1 f with H 2 O 2 showed first‐order dependences of the reaction rates on the concentrations of I (0.29–2.29 m M ), 1 f (0.04–0.29 M ), and H 2 O 2 (0.04–0.29 M ); see Figures S2 and S3 in the Supporting Information.…”

Section: Catalytic Oxidation Of Dimethylphenylsilane (1 A) With H2o2[a]mentioning

confidence: 62%

Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by a Lacunary Polyoxotungstate

2009

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Organosilicon compounds have attracted much attention, and silanols are widely utilized as building blocks for the production of silicon-based polymer materials and organic donors in metal-catalyzed cross-coupling reactions. [1, 2] Silanols are conventionally synthesized by hydrolysis of chlorosilanes [3] and treatment of siloxanes with alkaline reagents. [4] Strictly controlled reaction conditions are needed and it is difficult to synthesize sterically exposed silanols that readily condense to form disiloxanes. Oxidation with stoichiometric oxidants such as silver salts, [5] peracids, [6] permanganate, [7] dioxiranes, [8] osmium tetroxide, [9] oxaziridines, [10] and ozone [11] has also been reported. However, most of them lead to undesired production of the corresponding siloxanes instead of silanols. In contrast to these approaches, transitionmetal-catalyzed oxidation of silanes to silanols is a promising synthetic method. Hydrolytic oxidation systems based on Ir, [12] Ru, [13] Ag, [14] Cu, [15] Cr, [16] Re, [17] Pt, [18] and Au [19] catalysts with water as oxygen donor have been reported, and some of them show broad substrate scope and high catalytic activity. Another approach is oxidation of silanes by Re [20] and Tizeolite [21] catalysts with H 2 O 2 as oxygen donor. However, these systems have disadvantages: 1) applicability to a limited number of silanes, 2) use of an excess of highly concentrated H 2 O 2 or urea/H 2 O 2 adduct (UHP), 3) low turnover frequencies (TOF = 1-7), and 4) significant formation of undesirable siloxanes. Therefore, catalytic systems for efficient and selective H 2 O 2 -based oxidation of various silanes to silanols are scarcely known.Polyoxometalates have attracted considerable attention in the fields of structural chemistry, biological chemistry, catal-ysis, and materials science. [22] To date, numerous catalytic Figure 1. Polyhedral representation of the anion of (TBA) 4 [g-SiW 10 O 34 -(H 2 O) 2 ] (I). The {WO 6 } units and {SiO 4 } unit are shown as gray octahedra and a black tetrahedron, respectively. White octahedra indicate the tungsten atoms with aqua ligands.

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Section: Catalytic Oxidation Of Dimethylphenylsilane (1 A) With H2o2[a]mentioning

confidence: 62%

Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by a Lacunary Polyoxotungstate

2009

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“…In this regard, dioxiranes are capable of converting iodo compounds into the corresponding I(III) and I(V) species in a facile manner. For example, the treatment of aryl iodides such as iodobenzene (177) with 9 results in a mixture of hypervalent iodine compounds iodosobenzene (178) and iodylbenzene (179) in a 2 : 1 ratio (Scheme 42). 164 The reaction conditions were mild and operated under ambient conditions, whereas oxidation with KBrO 3 , NaIO 4 and Oxone® required heating.…”

Section: Applications Of Dioxiranes In Organic Synthesismentioning

confidence: 99%

“…This KIE is quite similar to the oxygenation of n Bu 3 SiH using carbene ( k H / k D = 1.23), whereas electrophilic ozone has a very different value ( k H / k D = 6.9). 175–177 Furthermore, product 190c displayed complete retention in configuration (Scheme 45a). Similar to carbene insertion, oxygenation of the Si–H bond with dioxiranes proceeds through an “oxene” mechanism via “butterfly-like” three-membered transition state 193 ( vide infra ).…”

Section: Applications Of Dioxiranes In Organic Synthesismentioning

confidence: 99%

Dioxiranes: a half-century journey

El‐Assaad¹,

Zhu²,

Sebastian³

et al. 2022

Org. Chem. Front.

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Silicon and Germanium Peroxides

Andō

2009

Patai's Chemistry of Functional Groups

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Introduction Preparation of Silyl Peroxides Reaction of Bis(Trimethylsilyl) Peroxides and Silyl Peroxosulfates Synthesis of Alcohols Via Hexa‐ and Pentacoordinate Silyl Peroxides Silane Ozonolysis: Silane Trioxides Cyclic Silyl Peroxides Germyl Peroxides

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The Ozone—Hydrosilane Reaction: A Mechanistic Study

Cited by 13 publications

References 0 publications

Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by a Lacunary Polyoxotungstate

Highly Selective Oxidation of Organosilanes to Silanols with Hydrogen Peroxide Catalyzed by a Lacunary Polyoxotungstate

Dioxiranes: a half-century journey

Silicon and Germanium Peroxides

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