Heterogeneously Catalysed Hydroamination

Sengupta, Manideepa; Das, Subhasis; Bordoloi, Ankur

doi:10.1002/cctc.202001394

Cited by 26 publications

(23 citation statements)

References 81 publications

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“…Various bases, additives and solvents were examined (see Supporting Information (SI) tables 1 and 2), and best conditions for the most satisfactory yield is as follow: on a 0.10-mmol scale, potassium tert-butoxide KO t Bu and diethoxymethylsilane Me(EtO)2SiH to be added at 50 mol% in 0.15 mL of DMPU solvent, heated at 30 o C over 18 hours. KO t Bu was revealed to be a superior base in promoting hydroamination in comparison to its alkali metal counterparts (Table 1, entries [4][5][6]. Additives like Fe(II) salts and inclusion of LiO t Bu (dual base system) proved to be detrimental for the system and led to diminished yields (see SI table 1).…”

Section: Scheme 1 Representative Strategies Employed For Alkene Hydroaminationmentioning

confidence: 99%

“…Numerous catalytic regimes for hydroamination of olefins have been developed over the years, ranging from those that utilise transition-metal homogeneous catalysts, 4 heterogeneous catalysts, 5 and photocatalysts, 6 to Brønsted acid 7 and base catalysts 1 (illustrated in Scheme 1, nonexhaustive). While base-catalysed hydroamination is generally more economical than transition-metal-based catalysis due to its higher atom-and cost-efficiency, strongly basic reagents (e.g., alkyllithium) and harsh conditions (e.g., high temperatures) are often employed.…”

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confidence: 99%

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Base-Mediated Site-Selective Hydroamination of Alkenes

Lee

Zhang

et al. 2021

Synthesis

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We present a base-mediated hydroamination protocol, using substoichiometric amounts of a hydrosilane and potassium tert-butoxide, that operates under mild conditions at 30 oC. Many aryl- and heteroatom-substituted olefins as well as aryl amines are tolerated, affording the desired products with complete regioselectivity. Preliminary mechanistic investigations reveal a non-radical pathway for hydroamination. A sequential remote hydroamination strategy involving an initial Fe-catalysed olefin isomerisation followed by our base-mediated hydroamination was also developed to directly access β-arylamines from terminal aliphatic alkenes.

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Section: Scheme 1 Representative Strategies Employed For Alkene Hydroaminationmentioning

confidence: 99%

mentioning

confidence: 99%

Base-Mediated Site-Selective Hydroamination of Alkenes

Lee

Zhang

et al. 2021

Synthesis

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“…For this purpose, we have explored two structures with Co 2+ In particular, the functional linkers in MOF matrices may enhance the stability of the immobilized Au-NPs as well as tune their catalytic activity and selectivity due to the specific electronic properties. 29 The sodalite (SOD) type ZIF-67 material with meim linkers (Co(meim) 2 , meim = 2-methylimidazolate) is an isostructural analog of the celebrated ZIF-8 (Zn(meim) 2 ) structure. However, unlike widely studied hybrid Au-NP@ZIF-8 systems, 26 there are only limited examples of the preparation of gold-containing nanomaterials based on ZIF-67.…”

Section: Introductionmentioning

confidence: 99%

“…In particular, the functional linkers in MOF matrices may enhance the stability of the immobilized Au-NPs as well as tune their catalytic activity and selectivity due to the specific electronic properties …”

Section: Introductionmentioning

confidence: 99%

Hydroamination of Phenylacetylene with Aniline over Gold Nanoparticles Embedded in the Boron Imidazolate Framework BIF-66 and Zeolitic Imidazolate Framework ZIF-67

Исаева

Papathanasiou

Чернышев

et al. 2021

ACS Appl. Mater. Interfaces

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The hydroamination of alkynes is an atom-economy process in the organic synthesis for the C–N bond formation, thereby allowing the production of fine chemicals and intermediates. However, direct interaction between alkynes and amines is complicated due to the electron enrichment of both compounds. Therefore, efficient hydroamination catalysts, especially heterogeneous ones, are in great demand. This work aimed at the development of novel heterogeneous catalysts based on zeolite-like metal–organic frameworks for phenylacetylene hydroamination. The sodalite (SOD) type zeolitic imidazolate framework ZIF-67 (Co(meim)2, meim = 2-methylimidazolate) and boron imidazolate framework BIF-66 ({Co[B(im)4]2}n, im = imidazolate) were studied as the carriers for the gold nanoparticles (Au-NPs). Au-NPs were embedded in the ZIF-67 and BIF-66 matrices by incipient wetness impregnation. Au@ZIF-67 and Au@BIF-66 hybrids were studied for the first time in the liquid phase hydroamination of phenylacetylene with aniline in an air atmosphere and have shown high activity and selectivity in respect to imine in this process. The pronounced impact of the nature of the metal–organic carrier, Au source, and reducing agent on the catalytic performance of the synthesized nanomaterials was found. To the best of our knowledge, it is the first example of using the zeolitic imidazolate framework and boron-imidazolate framework as the components of the gold-containing catalytic systems for the alkyne hydroamination.

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“…Further, the substrates of this reaction are easily-accessible. Hydroamidations are not spontaneous mainly due to the relatively high barrier of nucleophilic process 10 . Lewis-acid or transition metals are often used to catalyze this reaction.…”

Section: Introductionmentioning

confidence: 99%

Silylium ion Migration Dominated Hydroamidation of Siloxy-alkynes

Wang¹,

Jiang²,

Fan³

2021

Preprint

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Intermolecular hydroamidation of internal alkynes has been a long-standing challenge, one of the most successful examples so far is silver-catalyzed hydroamidation of siloxy-alkynes for which meet the standards of atom economic and mild reaction conditions of ideal hydroamidation. However, the mechanism of this reaction remains controversy. Using density function theory (DFT), we revealed that the reaction takes place through a silylium ion migration mediated hydroamidation (SMH) pathway. The SMH pathway goes through two steps, the first step is Ag+ promoted proton and silylium ion exchange between siloxy-alkynes and amide, leading to ketene and silyl-imines, the second step is Ag+ catalyzed nucleophilic addition between ketene and silyl-imines, following with a silylium ion migration afford the final product. In this reaction, Ag+ activate the siloxy-alkyne into silylium ion and silver-ketene through p-π conjugate effect, the silylium ion then act as catalyst. According to our calculation, the scopes of alkynes in this reaction may be extend to silyl-substituted ynamines or silyl-substituted ynamides, and the scopes of amide maybe expanded into p-π conjugate system such as diazoles, diazepines and so on. Our calculations also reveal a concise way to construct substituted enamides through Ag+ catalyzed nucleophilic addition between ketenes (or ketene imines) and silyl-substituted p-π conjugate system such as silyl-imines, silyl-diazoles.

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Heterogeneously Catalysed Hydroamination

Cited by 26 publications

References 81 publications

Base-Mediated Site-Selective Hydroamination of Alkenes

Base-Mediated Site-Selective Hydroamination of Alkenes

Hydroamination of Phenylacetylene with Aniline over Gold Nanoparticles Embedded in the Boron Imidazolate Framework BIF-66 and Zeolitic Imidazolate Framework ZIF-67

Silylium ion Migration Dominated Hydroamidation of Siloxy-alkynes

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