Pd-catalyzed synthesis of symmetrical and unsymmetrical siloxanes

Kurihara, Yu; Yamanoi, Yoshinori; Nishihara, Hiroshi

doi:10.1039/c3cc46294c

Cited by 21 publications

(12 citation statements)

References 48 publications

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“…This methodology allows easy and versatile synthesis of 16 Symmetrical disiloxanes are obtained from monomeric organoalkoxysilanes by hydrolysis, followed by condensation. However, there are few reports on the synthesis of unsymmetrical siloxanes with reactive functional groups.…”

Section: Transition Metal Catalyzed Synthesis Of Group 14 Compounds Vmentioning

confidence: 99%

Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Shimada

Yamanoi

Nishihara

2016

J. Synth. Org. Chem. Jpn.

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Extensive investigation of functional organosilicon and organogermanium compounds has identi ed various valuable applications in organic chemistry and advanced materials. This review summarizes the major developments of metal mediated coupling reactions between group 14 hydrides and organic halides during the last decade with an emphasis on our own studies. High reactivity and selectivity have been achieved for C Si and C Ge bond formations under mild conditions. This transformation shows good functional group compatibility, and can serve as a powerful tool for the synthesis of medicinal, pharmaceutical, agrochemical, electrical, and photoluminescent compounds. Ground and excited state properties of uorescence materials have been investigated by DFT and TD DFT calculations, and several important aspects of the experimental observations have been validated. Direct functionalization of H terminated Si and Ge surfaces has been demonstrated utilizing Pd mediated arylation reactions, illustrating the potential for further development of the Pd catalyzed reactions for the organic modi cation of semiconductor surfaces.

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Section: Transition Metal Catalyzed Synthesis Of Group 14 Compounds Vmentioning

confidence: 99%

Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Shimada

Yamanoi

Nishihara

2016

J. Synth. Org. Chem. Jpn.

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“…Reaction of an isolated aryl palladium iodide complex with a dihydrosilane (1:1 ratio)Scheme 52 A plausible catalytic cycle for the arylation of hydrosilanes with aryl halidesAdditionally, Yamanoi and Nishihara's research group have successfully extended this catalyst system to the synthesis of symmetrical and unsymmetrical siloxanes in yields of up to 82% via stepwise arylation of the corresponding siloxane bearing an Si-H bond (Scheme 53) 61. Palladium-catalyzed silylation of aryl halides with dihydrosilanes = OMe, 91% 106d, R = OH, 46% 106s, R = CN, 64% 106o, R = CF 3 , 76%…”

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confidence: 99%

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation

et al. 2015

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Arylsilanes are valuable organosilicon compounds and attract significant research interest due to their promising applications in organic synthesis. The development of aromatic C-Si cross-coupling reactions represents a major challenge in both organosilicon chemistry and organic synthesis. A number of investigations are focused on developing transition-metal-catalyzed Si-C coupling reactions due to the associated high atom economy and superior functional group compatibility. This review describes recent advances in transition-metal-catalyzed selective silylations of aryl C-H and C-X (X = halide) bonds with hydrosilanes.

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“…Catalytic routes toward unsymmetrical siloxanes (Si-O-Si') have also been demonstrated (Scheme 1, B, conditions VI-VIII) using Sc(OTf) 3 (Hreczycho et al, 2013;Hreczycho, 2015), Nafion (Kaźmierczak and Hreczycho, 2018), or Amberlyst-15 (Kuciński and Hreczycho, 2019a) with silanols and alkylsilanes at room temperature. Transition metal catalyzed routes to unsymmetrical disiloxanes have been achieved through Pd-catalyzed arylation of hydroxysiloxanes (Kurihara et al, 2013), nonhydrolytic Pd/Ccatalyzed cross-coupling reactions (Igarashi et al, 2014), Bamediated dehydrocoupling of hydrosilanes and silanols (Le Coz et al, 2019) and silylation of silanols catalyzed by a ruthenium complex (Marciniec et al, 2008). Other routes to form Si-O-Si' bonds include the use of fluoride and azidosilanes (Abele et al, 2003) as well as a catalyst-free, chlorine-free option using disilazanes (Kuciński and Hreczycho, 2019b) (Scheme 1, B, conditions IX-X).…”

Section: Introductionmentioning

confidence: 99%

Catalytic Synthesis of Oligosiloxanes Mediated by an Air Stable Catalyst, (C6F5)3B(OH2)

et al. 2020

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The utility of (C 6 F 5) 3 B(OH 2) as catalyst for the simple and environmentally benign synthesis of oligosiloxanes directly from hydrosilanes, is reported. This protocol offers several advantages compared to other methods of synthesizing siloxanes, such as mild reaction conditions, low catalyst loading, and a short reaction time with high yields and purity. The considerable H 2 O-tolerance of (C 6 F 5) 3 B(OH 2) promoted a catalytic route to disiloxanes which showed >99% conversion of three tertiary silanes, Et 3 SiH, PhMe 2 SiH, and Ph 3 SiH. Preliminary data on the synthesis of unsymmetrical disiloxanes (Si-O-Si') suggests that by modifying the reaction conditions and/or using a 1:1 combination of silane to silanol the cross-product can be favored. Intramolecular reactions of disilyl compounds with catalytic (C 6 F 5) 3 B(OH 2) led to the formation of novel bridged siloxanes, containing a Si-O-Si linkage within a cyclic structure, as the major product. Moreover, the reaction conditions enabled recovery and recycling of the catalyst. The catalyst was re-used 5 times and demonstrated excellent conversion for each substrate at 1.0 mol% catalyst loading. This seemingly simple reaction has a rather complicated mechanism. With the hydrosilane (R 3 SiH) as the sole starting material, the fate of the reaction largely depends on the creation of silanol (R 3 SiOH) from R 3 SiH as these two undergo dehydrocoupling to yield a disiloxane product. Generation of the silanol is based on a modified Piers-Rubinsztajn reaction. Once the silanol has been produced, the mechanism involves a series of competitive reactions with multiple catalytically relevant species involving water, silane, and silanol interacting with the Lewis acid and the favored reaction cycle depends on the concentration of various species in solution.

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Pd-catalyzed synthesis of symmetrical and unsymmetrical siloxanes

Cited by 21 publications

References 48 publications

Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation

Catalytic Synthesis of Oligosiloxanes Mediated by an Air Stable Catalyst, (C6F5)3B(OH2)

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Pd-catalyzed synthesis of symmetrical and unsymmetrical siloxanes

Cited by 21 publications

References 48 publications

Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation­ Synchronized with Si–H Bond Activation

Catalytic Synthesis of Oligosiloxanes Mediated by an Air Stable Catalyst, (C6F5)3B(OH2)

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Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation