Oxyfunctionalization reactions by perfluoro cis-2,3-dialkyloxaziridines. Enantioselective conversion of silanes into silanols

Cavicchioli, Marcello; Montanari, Vittorio; Resnati, Giuseppe

doi:10.1016/s0040-4039(00)73424-1

Cited by 58 publications

(34 citation statements)

References 5 publications

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“…Whilst less bulky silanols can be synthesized by hydrolysis of chlorosilanes under strictly controlled conditions, it is difficult to synthesize sterically hindered silanols, silanediols, and silanols with functional groups sensitive to hydrolytic conditions . Silanols can also be synthesized by oxidation of organosilanes, with strong oxidants, such as silver salts, permanganate, osmium tetroxide, dioxiranes, peracids, oxaziridines, and ozone ,. Apart from generating stochiometric amounts of waste, these methods are often accompanied with problems of selectivity, for example, producing undesired siloxanes by condensation of two molecules of silanol, or byproducts resulting from silanol decomposition .…”

Section: Methodsmentioning

confidence: 99%

Selective Manganese‐Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions

et al. 2019

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The first manganese‐catalyzed oxidation of organosilanes to silanols with H2O2 under neutral reaction conditions has been accomplished. A variety of organosilanes with alkyl, aryl, alknyl, and heterocyclic substituents were tolerated, as well as sterically hindered organosilanes. The oxidation appears to proceed by a concerted process involving a manganese hydroperoxide species. Featuring mild reaction conditions, fast oxidation, and no waste byproducts, the protocol allows a low‐cost, eco‐benign synthesis of both silanols and silanediols.

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Section: Methodsmentioning

confidence: 99%

Selective Manganese‐Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions

et al. 2019

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“…Early reports involve the use of stoichiometric oxidants. Pioneering attempts by Adam, Mello, and Curci promote the use of dioxiranes for this transformation, whereas Resnati demonstrates the oxidation of organosilanes by utilizing polyfluorooxaziridine . In 2013, Kokotos and co‐workers proposed an organocatalytic oxidation of organosilanes to silanols by using 2,2,2‐trifluoroacetophenone as the catalyst and H 2 O 2 as the oxidant (Scheme ) …”

Section: Other Oxidation Reactions and Mechanistic Studiesmentioning

confidence: 99%

Green Organocatalytic Oxidative Methods using Activated Ketones

2018

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Alkenes are very important moieties in organic chemistry and have been employed as starting materials for the synthesis of important organic compounds. In this review, we present organocatalytic reactions in which alkenes play a central role, especially their organocatalytic oxidation to epoxides. This topic plays a pivotal role in our recent research, for which we utilize H2O2 as a green oxidant and a ketone as the catalyst. Extension to other oxidative transformations is also presented.

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“…(3); α‐Np=α‐naphthyl]. Such a high retention of configuration is also observed with stoichiometric oxidants such as m ‐chloroperbenzoic acid ( m ‐CPBA, 86 % ee ),6a dimethyldioxirane (98 % ee ),8 and oxaziridines (99 % ee ),10 as well as catalytic MTO/UHP (94 % ee ),20a for which concerted transition‐state structures are proposed. On the other hand, oxidation of 1 p proceeds with inversion of configuration at the silicon center in hydrolytic oxidation with [{RuCl 2 ( p ‐cymene)} 2 ] (67 % ee )13a and Ru‐HAP (97 % ee ),13b for which nucleophilic attack of water on a silyl metal hydride intermediate has been proposed. …”

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

confidence: 79%

“…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 ozone11 has also been reported. However, most of them lead to undesired production of the corresponding siloxanes instead of silanols.…”

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

confidence: 99%

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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Oxyfunctionalization reactions by perfluoro cis-2,3-dialkyloxaziridines. Enantioselective conversion of silanes into silanols

Cited by 58 publications

References 5 publications

Selective Manganese‐Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions

Selective Manganese‐Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions

Green Organocatalytic Oxidative Methods using Activated Ketones

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

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