Highly Selective Hydroxylation and Alkoxylation of Silanes: One-Pot Silane Oxidation and Reduction of Aldehydes/Ketones

Luo, Nianhua; Liao, Jianhua; Ouyang, Lu; Wen, Hang; Zhong, Yuhong; Liu, Jitian; Tang, Weiping; Luo, Renshi

doi:10.1021/acs.organomet.9b00716

Cited by 32 publications

(13 citation statements)

References 48 publications

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“…Recently, we have strong interest in the design and synthesis of bis‐nitrogen iridium complexes and their catalytic reactions. As our continuous effort in the development of iridium complexes‐catalyzed organic transformation reactions, we developed the pH‐dependent chemoselective transfer hydrogenation of α,β‐unsaturated aldehydes [ 27 ] and selective hydroxylation and alkoxylation of silanes [ 28 ] (Scheme 1a). In our previous work, we found Tang's catalysts can efficiently catalyze the decomposition of formic acid to release carbon dioxide and hydrogen.…”

Section: Methodsmentioning

confidence: 99%

One‐Pot Transfer Hydrogenation Reductive Amination of Aldehydes and Ketones by Iridium Complexes “on Water”

et al. 2020

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An efficient and practical one‐pot transfer hydrogenation reductive amination of aldehydes and ketones with amines has been developed by using iridium complexes as catalysts and formic acid as hydrogen source in aqueous solution, providing an environmentally friendly methodology for the construction of a wide range of functionalized amine compounds in excellent yields (≈ 80 %‐95 %). This effective methodology can be scaled up to gram scale with 0.1 mol‐% catalyst loading and also be employed in the synthesis of medical substances such as Meclizine.

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Section: Methodsmentioning

confidence: 99%

One‐Pot Transfer Hydrogenation Reductive Amination of Aldehydes and Ketones by Iridium Complexes “on Water”

et al. 2020

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“…This fact reinforces the idea of an Ir−THF⇌Ir−OH 2 equilibrium. No hydrogen evolution was observed during these experiments, therefore, a mechanism operating through Ir III ‐OH intermediates, as proposed by Luo et al., [38] can be excluded. To study the ability of complex 1 to activate Et 3 Si−H, as proposed within the electrophilic mechanism, compound 1 was reacted with 10 equivalents of Et 3 Si−H in THF‐d 8 .…”

Section: Resultsmentioning

confidence: 53%

Hydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silanes

et al. 2022

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An unprecedented quantum tunneling effect has been observed in catalytic SiÀ H bond activations at room temperature. The cationic hydrido-silyl-iridium-4 ], has proven to be a highly efficient catalyst for the hydrolysis and the alcoholysis of organosilanes. When triethylsilane was used as a substrate, the system revealed the largest kinetic isotopic effect (KIE SiÀ H/SiÀ D = 346 � 4) ever reported for this type of reaction. This unexpectedly high KIE, measured at room temperature, together with the calculated Arrhenius preexponential factor ratio (A H /A D = 0.0004) and difference in the observed activation energy [(E a D À E a H ) = 34.07 kJ mol À 1 ] are consistent with the participation of quantum tunneling in the catalytic process. DFT calculations have been used to unravel the reaction pathway and identify the rate-determining step. Aditionally, isotopic effects were considered by different methods, and tunneling effects have been calculated to be crucial in the process.

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“…The spectroscopic data are in agreement with those reported in the literature. [46] Triphenylsilanol (6 k): [CAS 791-31-1]: M.p. 154.…”

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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Highly Selective Hydroxylation and Alkoxylation of Silanes: One-Pot Silane Oxidation and Reduction of Aldehydes/Ketones

Cited by 32 publications

References 48 publications

One‐Pot Transfer Hydrogenation Reductive Amination of Aldehydes and Ketones by Iridium Complexes “on Water”

One‐Pot Transfer Hydrogenation Reductive Amination of Aldehydes and Ketones by Iridium Complexes “on Water”

Hydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silanes

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

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