Ruthenium-Catalyzed Dual Dehydrogenative Silylation of C(sp<sup>3</sup>)–H Bonds: Access to Diverse Silicon-Centered Spirocycles

Wang, Zichen; Fang, Huaquan; Liu, Guixia; Huang, Zheng

doi:10.1021/acs.orglett.1c02821

Cited by 11 publications

(4 citation statements)

References 36 publications

(14 reference statements)

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“…Following protection of o-bromophenol, a one-pot multistep reaction was employed (Figure 38). 108 Silyl ether 27b was reacted with magnesium turnings and I2 to form a Grignard reagent (28). The resulting reaction mixture was reacted with tetraethoxysilane, which acted as the electrophile to form a triethoxyarylsilane intermediate (29).…”

Section: Hydroxy Hydrogen-bond Donormentioning

confidence: 99%

“…Following the protection of phenol into a silyl ether, another one-pot multistep procedure was taken via an ortho-lithiation (Figure 40). 108 The protected phenol (31a and 31b) was reacted with nBuLi to deprotonate the ortho-position. The lithiated intermediate was reacted with 1 equivalent of SiCl4 to form a dichlorodiaryl intermediate (32), which could be reduced using LiAlH4 to form a dihydrosilane (33).…”

Section: Hydroxy Hydrogen-bond Donormentioning

confidence: 99%

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Synthesis of Organosilanes and Investigation of Their Catalytic Activity for Direct Amide Bond Formation

D'Amaral

2024

Preprint

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<p>Amide synthesis is a fundamental reaction in synthetic chemistry due to the abundance of amides in biologically active molecules, synthetic polymers, and commercial products. Coupling reagents that activate the carboxylic acid have become the most well-studied method to direct amide bond formation. Amongst these, carbodiimides, uronium and phosphonium salts, and benzotriazoles are the most common. These reactions, however, are often limited by poor atom economy, and toxic and expensive reagents. Therefore, synthetic chemists need a better method to form amides safely and efficiently. Organosilanes have been reported as greener, efficient alternative amide coupling reagents. Current work in this field often requires a stoichiometric (or more) amount of the silane. While stoichiometric amide coupling reactions are generally the methods of choice for their efficiency and practicality, catalytic amide coupling can present a new step toward greener methodologies to make amides. This thesis explores novel organosilanes that are investigated as catalysts for direct amidation. The silane catalysts are designed to have enhanced reactivity by incorporating a hydrogen bond donor (HBD) to facilitate the formation of a silyl ester intermediate and nucleophilic attack at the carbonyl by the amine coupling partner. The synthesis of various organosilanes have been investigated, including silanes that have an amide or urea, hydroxy, or protonated amine as a HBD. The silanes that have been successfully synthesized were tested as catalysts in direct amidation. Aryl and alkyl silanes, and di- and trisubstituted silanes were used in stoichiometric silane-mediated amide synthesis to study how the substitution on the silicon effects amidation.</p>

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Section: Hydroxy Hydrogen-bond Donormentioning

confidence: 99%

Section: Hydroxy Hydrogen-bond Donormentioning

confidence: 99%

Synthesis of Organosilanes and Investigation of Their Catalytic Activity for Direct Amide Bond Formation

D'Amaral

2024

Preprint

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“…In 2021, Huang, Liu and coworkers constructed silaspiranes 36 through dehydrogenative silylation of the C( sp 3 )−H bond α to the O, N or C atoms (Scheme 10). [22] Bis(phosphine)‐based pincer Ru complex (PCP)‐RuH(NBD) 35 , which was developed in the their group, functioned well to catalyze the C( sp 3 )−H silylation of dihydrosilanes 34 . The reaction showed a good generality for the synthesis of unprecedented oxa ‐spirosilabiindanes ( 36 a – 36 e , 36 g ) and aza ‐spirosilabiindanes ( 36 h ).…”

Section: Cyclizationmentioning

confidence: 99%

Recent Progress in the Synthesis of Silaspiranes

Chen,

Hu,

Wang

et al. 2023

Chemistry A European J

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Silaspiranes bearing a spiro‐silicon center are promising ring frameworks for the synthesis of novel spirocyclic molecules possessing unique properties. Development of efficient methods towards these ring structures has therefore attracted considerable attentions of synthetic chemists. This minireview highlights the representative advances in the field, and is categorized into four parts according to the ring formation strategies: cyclization, annulation, ring expansion and cycloaddition.

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“…Recently, Huang & Liu group reported a rare pincer Ru‐catalyzed dual intramolecular dehydrogenative silylation of primary C(sp 3 )−H bonds accessed to diverse silicon‐centered spirocycles (Scheme 31(b)) [49] . The reaction system exhibited excellent regioselectivity, silylation selective took place at C(sp 3 )−H α to C, O, N atoms.…”

Section: Dihydrosilane‐mediated C−h Silylationmentioning

confidence: 99%

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

Kong

2022

Chemistry An Asian Journal

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Organosilicon compounds are widely used in materials science, medicinal chemistry and synthetic chemistry. Recently, significant progress has been achieved in transition metal‐catalyzed dehydrogenative C−H silylation. Particularly, recently developed monohydrosilane and dihydrosilane mediated C−H silylation have emerged as powerful tools in constructing C−Si bonds. Besides, dihydrosilane‐mediated enantioselective asymmetric C−H silylation has successfully enabled the construction of central and helical silicon chirality. In addition, chiral organosilicon compounds have exhibited excellent photoelectric material properties and broad application prospects. Furthermore, organosilicon compounds could under a series of functional group transformations to enrich the diversity of silicon chemistry. This review will present a comprehensive picture of the development of transition metal‐catalyzed hydrosilane‐mediated intramolecular C(sp2)−H and C(sp3)−H silylation organized by their reaction types and mechanisms. In addition, dihydrosilane‐mediated enantioselective asymmetric C−H silylation to construct central and helical silicon chirality will also be highlighted in the review.

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Ruthenium-Catalyzed Dual Dehydrogenative Silylation of C(sp³)–H Bonds: Access to Diverse Silicon-Centered Spirocycles

Cited by 11 publications

References 36 publications

Synthesis of Organosilanes and Investigation of Their Catalytic Activity for Direct Amide Bond Formation

Synthesis of Organosilanes and Investigation of Their Catalytic Activity for Direct Amide Bond Formation

Recent Progress in the Synthesis of Silaspiranes

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

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Ruthenium-Catalyzed Dual Dehydrogenative Silylation of C(sp3)–H Bonds: Access to Diverse Silicon-Centered Spirocycles

Cited by 11 publications

References 36 publications

Synthesis of Organosilanes and Investigation of Their Catalytic Activity for Direct Amide Bond Formation

Synthesis of Organosilanes and Investigation of Their Catalytic Activity for Direct Amide Bond Formation

Recent Progress in the Synthesis of Silaspiranes

Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

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Product

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Ruthenium-Catalyzed Dual Dehydrogenative Silylation of C(sp³)–H Bonds: Access to Diverse Silicon-Centered Spirocycles