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

Wang, Kaikai; Zhou, Jimei; Jiang, Yuting; Zhang, Miaomiao; Wang, Chao; Duan, Xue; Tang, Weijun; Sun, Huamin; Xiao, Jianliang; Li, Chaoqun

doi:10.1002/anie.201900342

Cited by 54 publications

(42 citation statements)

References 60 publications

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“…It is worth noting that alkenyl‐ and alkynyl‐substituted hydrosilanes underwent this transformation smoothly to afford silanols 29 and 30 . As for 29 , epoxidation of the C=C bond was not observed [8f] . Interestingly, a substrate having two Si−H bonds could be completely transformed into the corresponding silanediol 31 in a reasonable yield.…”

Section: Resultsmentioning

confidence: 92%

“…Transition‐metal catalysis has provided an attractive alternative to access silanols. Several metal catalysts, such as Ti, [8a] Re, [8b] W, [8c] Te, [8d] Co, [8e] and Mn, [8f] have been exploited to convert hydrosilanes to silanols with H 2 O 2 or O 2 as an oxidant (Scheme 1 a, top). Water is a more appealing oxygen donor because of its safety (non‐toxic, non‐explosive, and non‐flammable) and its abundant and inexpensive character.…”

Section: Introductionmentioning

confidence: 99%

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Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations

Liang

Wang

et al. 2020

Angewandte Chemie

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The first electrochemical hydrolysis of hydrosilanes to silanols under mild and neutral reaction conditions is reported. The practical protocol employs commercially available and cheap NHPI as ah ydrogen-atom transfer (HAT) mediator and operates at room temperature with high selectivity,leading to various valuable silanols in moderate to good yields.N otably,t his electrochemical method exhibits ab road substrate scope and high functional-group compatibility,and it is applicable to late-stage functionalization of complex molecules.Preliminary mechanistic studies suggest that the reaction appears to proceed through anucleophilic substitution reaction of an electrogenerated silyl cation with H 2 O.

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Section: Resultsmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations

Liang

Wang

et al. 2020

Angewandte Chemie

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“…73.6-74.3 °C; IR (ATR) ν = 3300 (br), 3052,3015,2971,2922,2878,1953,1924,1748,1599,1504,1453,1406,1363,1322,1275,1166,1123,1071,1023,950,900,861,822,772,740,703,641, 619 cm À 1 ; 1 H NMR (500 MHz, CDCl 3 ): δ = 1.59 (d, J = 6.3 Hz, 3 H), 1.92 (br s, 1 H), 5.08 (q, J = 6.1 Hz, 1 H), 7. 44-7.54 (m, 3 H), 7.80-7.87 (m, 4 H (10), 129 (100), 128 (82), 127 (47), 126 (18), 115 (8), 102 (11), 77 (8), 75 (9), 74 (8), 63 (10), 43 (14); elemental analysis (%) calcd for C 12 H 12 O: C 83.69, H 7.02; found: C 83.84, H 7.11. The spectroscopic data are in agreement with those reported in the literature. [12,14,45] Triphenylethoxysilane (5 k): [CAS 1516-80-9]: M.p.…”

Section: -(Naphthalenmentioning

confidence: 99%

“…37-7.42 (m, 6 H), 7.43-7.47 (m, 3 H), 7.62-7.66 (m, 6 H); 13 C NMR and DEPT (151 MHz, CDCl 3 ): δ = 128.08 (6 CH),130.28 (3 CH),135.12 (6 CH),135.25 (3 C); MS (EI): m/z (%) = 276 (48, [M] + ), 200 (19), 199 (100), 197 (16), 181 (12), 152 (11), 122 (15), 77 (22), 51 (13); elemental analysis (%) calcd for C 18 H 16 OSi: C 78.22,H 5.83;found: C 78.37,H 5.87. The spectroscopic data are in agreement with those reported in the literature. [47]…”

Section: -(Naphthalenmentioning

confidence: 99%

Mechanistic Studies on the Hexadecafluorophthalocyanine–Iron‐Catalyzed Wacker‐Type Oxidation of Olefins to Ketones**

Puls

Seewald

Grinenko

et al. 2021

Chemistry A European J

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The hexadecafluorophthalocyanine-iron complex FePcF 16 was recently shown to convert olefins into ketones in the presence of stoichiometric amounts of triethylsilane in ethanol at room temperature under an oxygen atmosphere. Herein, we describe an extensive mechanistic investigation for the conversion of 2-vinylnaphthalene into 2-acetylnaphthalene as model reaction. A variety of studies including deuterium-and 18 O 2 -labeling experiments, ESI-MS, and 57 Fe Mössbauer spectroscopy were performed to identify the intermediates involved in the catalytic cycle of the oxidation process. Finally, a detailed and well-supported reaction mechanism for the FePcF 16 -catalyzed Wacker-type oxidation is proposed.

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“…Recently, the selective oxygenase-type oxidation of silanes to silanols using O 2 with engineered cytochrome P450 enzymes has been reported (Fig. 1B, II) 21 . Unfortunately, the reported catalytic activity is extremely dependent on the reaction conditions, and the associated high costs can be a significant limitation for large-scale synthesis.…”

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confidence: 99%

Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

Cao

Zhang²,

Peng

et al. 2022

Preprint

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Development of biomimetic catalytic systems that can imitate or even surpass natural enzymes remains an ongoing challenge 1–3. This is particularly true in the context of accessing non-natural reactions by bioinspired approaches, which offer intriguing possibilities for benign and affordable chemical synthesis 4. Exploiting the untapped potential of inorganic solids by translating complex knowledge in (bio)molecular-based systems may constitute a potentially useful strategy for such purpose 5, but efforts to capitalize on the minimum catalytic unit of a versatile solid matrix have been largely unsuccessful. Here, we show how an all-inorganic biomimetic system bearing robust nitrogen-neighboured single cobalt site/pyridinic-N site (Co-N4/Py-N) pairs can act cooperatively as an oxidase mimic, which renders an engaged coupling of oxygen (O2) reduction with synthetically beneficial chemical transformations. By developing this broadly applicable platform, the scalable synthesis of greater than 100 industrially and pharmaceutically appealing O-silylated compounds via the unprecedented aerobic oxidation of hydrosilane under ambient conditions is demonstrated. Moreover, this heterogeneous oxidase mimic also offers potential for expanding the catalytic scope of enzymatic synthesis. We anticipate that the strategy demonstrated here will pave a new avenue for understanding the underlying nature of redox enzymes and open up a new class of material systems for artificial biomimetics.

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

Cited by 54 publications

References 60 publications

Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations

Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations

Mechanistic Studies on the Hexadecafluorophthalocyanine–Iron‐Catalyzed Wacker‐Type Oxidation of Olefins to Ketones**

Nitrogen-neighboured single cobalt sites enable heterogeneous oxidase-type catalysis

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