Photoactivated silicon–oxygen and silicon–nitrogen heterodehydrocoupling with a commercially available iron compound

Reuter, Matthew B.; Cibuzar, Michael P.; Hammerton, A. James; Waterman, Rory

doi:10.1039/c9dt04870g

Cited by 21 publications

(23 citation statements)

References 51 publications

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“…The iron dimer [Cp(CO) 2 Fe] 2 ( 17 ) couples primary and secondary amines with primary and secondary silanes, with amine basicity proposed as an influencing factor [40] . Photoactivation of 17 under visible‐light irradiation produces 2 equiv of the transient 17 e− species Cp(CO) 2 Fe • ( 18 ).…”

Section: D‐block Catalystsmentioning

confidence: 99%

“… Proposed mechanism for the heterodehydrocoupling of silanes and amines by 17 under visible‐light irradiation [40] …”

Section: D‐block Catalystsmentioning

confidence: 99%

“…[20a] The iron dimer [Cp(CO) 2 Fe] 2 (17)c ouples primary and secondary amines with primary and secondary silanes, with amine basicity proposed as an influencing factor. [40] Photoactivation of 17 under visible-light irradiationp roduces 2equivo ft he transient1 7eÀ species Cp(CO) 2 Fe * (18). Isolated iron-silyl derivatives (19)w ere found to be catalytically incompetent, and a nucleophilic Cp(CO) 2 FeNR 2 (20)w as proposed as the SiÀN bond forming intermediate (Scheme1 1).…”

Section: D-block Catalystsmentioning

confidence: 99%

“…Proposed mechanism for the heterodehydrocoupling of silanes and amines by 17 under visible-light irradiation. [40] Scheme12. Proposed mechanism for the heterodehydrocoupling of silanes and amines by Webster and co-workers.…”

Section: D-block Catalystsmentioning

confidence: 99%

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Silicon–Nitrogen Bond Formation via Heterodehydrocoupling and Catalytic N‐Silylation

Reuter

Hageman

Waterman

2020

Chemistry A European J

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Silicon–nitrogen bond formation is an important subfield in main group chemistry, and catalysis is an attractive route for efficient, selective formation of these bonds. Indeed, heterodehydrocoupling and N‐silylation offer facile methods for the synthesis of small molecules through the coupling of primary, secondary, and tertiary silanes with N‐containing substrates such as amines, carbazoles, indoles, and pyrroles. However, the reactivity of these catalytic systems is far from uniform, and critical issues are often encountered with product selectivity, conversions, substrate scope, catalyst activation, and in some instances, competing side reactions. Herein, a catalogue of catalysts and their reactivity for Si−N heterodehydrocoupling and N‐silylation are reported.

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Section: D‐block Catalystsmentioning

confidence: 99%

“… Proposed mechanism for the heterodehydrocoupling of silanes and amines by 17 under visible‐light irradiation [40] …”

Section: D‐block Catalystsmentioning

confidence: 99%

Section: D-block Catalystsmentioning

confidence: 99%

Section: D-block Catalystsmentioning

confidence: 99%

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Silicon–Nitrogen Bond Formation via Heterodehydrocoupling and Catalytic N‐Silylation

Reuter

Hageman

Waterman

2020

Chemistry A European J

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“…[6][7][8][9][10] to their most known function as a temporary protective group for hydroxyl moieties (e.g., natural products synthesis, derivatization, etc.). [11][12][13][14] There are several methods of their synthesis, starting with classical condensation between alcohols and halosilanes, [15] and finishing on catalytic coupling reactions with hydro-, [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] vinyl- [33] or allylsilanes, [34,35] and more recently also with silyl formates. [36][37][38] However, in the case of O-silylation of alcohols with alkynylsilanes -this process has never been comprehensively studied, and previous investigations have mainly referred to the problem of C sp -Si bond stability rather than the application of this transformation as an efficient method for obtaining silyl ethers.…”

Section: Introductionmentioning

confidence: 99%

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

2020

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The formation of several silyl ethers (alkoxysilanes, R3Si‐OR') and unsymmetrical siloxanes (R3Si‐O‐SiR'3) can be catalyzed by the commercially available potassium bis(trimethylsilyl)amide (KHMDS). The reaction proceeds via direct dealkynative coupling between various alcohols or silanols and alkynylsilanes, with a simultaneous formation of gaseous acetylene as the sole by‐product. The dehydrogenative and dealkenative coupling of alcohols or silanols are well‐investigated, whilst the utilization of alkynylsilanes as silylating agents has never been comprehensively studied in this context. Overall, the presented system allows the synthesis of various attractive organosilicon compounds under mild conditions, making this approach an atom‐efficient, environmentally benign, and sustainable alternative to existing synthetic solutions.

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Phenylsilane

Yang,

Ali,

Radosevich

2024

Encyclopedia of Reagents for Organic Synthesis

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image [694‐53‐1] C 6 H 5 SiH 3 (MW 108.22) InChI = 1S/C6H8Si/c7‐6‐4‐2‐1‐3‐5‐6/h1‐5H,7H3 InChiKey = PARWUHTVGZSQPD‐UHFFFAOYSA‐N (reagent used as reductant in catalysis) Physical Data : bp 120 °C (750 torr) 1 ; density = 0.8775 g mL −2 . Solubility : soluble in most organic solvents; releases flammable gas upon contact with water. Form Supplied : clear, colorless oil, commercially available. Analysis of Reagent Purity : purity is analyzed by 1 H NMR (500 MHz, CD 2 Cl 2 ): δ 4.19 (s, 3 H ), 7.36–7.41 (m, 3 H ), 7.37 (d, J = 7.6 Hz, 2 H ); 13 C{1 H } NMR (126 MHz, CD 2 Cl 2 ): δ 128.7 (s, 2C), 130.4 (s), 136.2 (s), 136.4 (s, 2C), and 29 Si DEPT NMR (99 MHz, CD 2 Cl 2 ) δ −59.8. 2 Preparative Method : reduction of phenyltrichlorosilane or phenyltriethoxysilane with lithium aluminum hydride in ether. 1,3 Purification : distillation under nitrogen at room temperature and atmospheric pressure. 4 Handling, Storage, and Precautions : flammable. Stable at room temperature in closed containers. Phenylsilane is capable of releasing hydrogen gas upon storage, particularly in the presence of acids, bases, or fluoride‐releasing salts. 5 Precautions should be taken to vent possible hydrogen buildup when opening vessels in which phenylsilane is stored.

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Photoactivated silicon–oxygen and silicon–nitrogen heterodehydrocoupling with a commercially available iron compound

Abstract: A commercially available iron readily engages in catalytic Si–O and Si–N bond formation under visible light irradiation.

Cited by 21 publications

References 51 publications

Silicon–Nitrogen Bond Formation via Heterodehydrocoupling and Catalytic N‐Silylation

Silicon–Nitrogen Bond Formation via Heterodehydrocoupling and Catalytic N‐Silylation

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

Phenylsilane

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