Direct synthesis of alkylsilanes by platinum-catalyzed coupling of hydrosilanes and iodoalkanes

Inubushi, Hikaru; Kondo, Hitoshi; Lesbani, Aldes; Miyachi, Mariko; Yamanoi, Yoshinori; Nishihara, Hiroshi

doi:10.1039/c2cc35150a

Cited by 27 publications

(16 citation statements)

References 46 publications

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“…Among them, arylsilanes continue to be important because they are key components for new organic functional materials. These compounds can be prepared by the reaction of aryl Grignard or aryl lithium reagents with halosilanes,2 and transition‐metal‐catalyzed coupling reaction of aryl halides with hydrosilanes3 or disilanes 4. However, dehydrogenative silylation of simple arenes with hydrosilanes through both CH and SiH bond activation would be a more direct and attractive because of atom‐efficiency and environmental benignity 5.…”

Section: Optimization Of Reaction Conditionsmentioning

confidence: 99%

Iridium‐Catalyzed Intermolecular Dehydrogenative Silylation of Polycyclic Aromatic Compounds without Directing Groups

Murai¹,

Takami²,

Takai³

2015

Chemistry A European J

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This study describes the iridium-catalyzed intermolecular dehydrogenative silylation of C(sp(2))-H bonds of polycyclic aromatic compounds without directing groups. The reaction produced various arylsilanes through both Si-H and C-H bond activation, with hydrogen as the sole byproduct. Reactivity was affected by the electronic nature of the aromatic compounds, and silylation of electron-deficient and polycyclic aromatic compounds proceeded efficiently. Site-selectivity was controlled predominantly by steric factors. Therefore, the current functionalization proceeded with opposite chemo- and site-selectivity compared to that observed for general electrophilic functionalization of aromatic compounds.

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Section: Optimization Of Reaction Conditionsmentioning

confidence: 99%

Iridium‐Catalyzed Intermolecular Dehydrogenative Silylation of Polycyclic Aromatic Compounds without Directing Groups

Murai¹,

Takami²,

Takai³

2015

Chemistry A European J

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“…Among the versatile developed synthetic methods, palladium‐catalyzed silicon–carbon cross‐coupling through dehalogenative coupling of aryl halide (Scheme ) with hydrosilane has attracted much attention, owing to its superior functional group comparability and improved atom economy. Many examples of palladium‐catalyzed silylation of aryl halides with various hydrosilanes, including di‐ or triorganosilanes, trialkoxysilanes, hydrooligosilanes, and hydrosiloxane, have been reported. Recently, this reaction was further applied to synthesis of the challenging silicon‐centered chiral silane through the desymmetrization of dihydrosilanes with aryl halides .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Zhang

et al. 2017

Chemistry An Asian Journal

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The catalytic cycles of palladium-catalyzed silylation of aryl iodides, which are initiated by oxidative addition of hydrosilane or aryl iodide through three different mechanisms characterized by intermediates R Si-Pd -H (Cycle A), Ar-Pd -I (Cycle B), and Pd (Cycle C), have been explored in detail by hybrid DFT. Calculations suggest that the chemical selectivity and reactivity of the reaction depend on the ligation state of the catalyst and specific reaction conditions, including feeding order of substrates and the presence of base. For less bulky biligated catalyst, Cycle C is energetically favored over Cycle A, through which the silylation process is slightly favored over the reduction process. Interestingly, for bulky monoligated catalyst, Cycle B is energetically more favored over generally accepted Cycle A, in which the silylation channel is slightly disfavored in comparison to that of the reduction channel. Moreover, the inclusion of base in this channel allows the silylated product become dominant. These findings offer a good explanation for the complex experimental observations. Designing a reaction process that allows the oxidative addition of palladium(0) complex to aryl iodide to occur prior to that with hydrosilane is thus suggested to improve the reactivity and chemoselectivity for the silylated product by encouraging the catalytic cycle to proceed through Cycles B (monoligated Pd catalyst) or C (biligated Pd catalyst), instead of Cycle A.

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“…In the presence of Pt(P(t Bu) 3 ) 2 , coupling reactions of tertiary silanes with 1 iodoalkane provided alkylated quaternary silanes in good yield (39 43). 20 This reaction worked well for a broad range of functional groups such as ester and cyano moieties (44 and 45). To highlight its practical utility, we used it in the synthesis of sila uofen (46), an agricultural insecticide.…”

Section: )mentioning

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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Direct synthesis of alkylsilanes by platinum-catalyzed coupling of hydrosilanes and iodoalkanes

Abstract: Alkyl iodides and tertiary silanes were successfully coupled with good functional group tolerance using a Pt(P(tBu)(3))(2)/(iPr)(2)EtN/CH(3)CN system. The utility of the methodology is demonstrated by the synthesis of silafluofen, a Si-containing insecticide.

Cited by 27 publications

References 46 publications

Iridium‐Catalyzed Intermolecular Dehydrogenative Silylation of Polycyclic Aromatic Compounds without Directing Groups

Iridium‐Catalyzed Intermolecular Dehydrogenative Silylation of Polycyclic Aromatic Compounds without Directing Groups

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

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

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