Iron/Caffeine as a Catalytic System for Microwave‐Promoted Benzamide Formation

Bantreil, Xavier; Navals, Pauline; Martinez, Jean

doi:10.1002/ejoc.201403173

“…Steric hindrance had a strong influence on the amidation reaction, since N-tertbutyl benzamide 3d was isolated in only 42% yield. Importantly, the turnover number (TON) and turnover frequency (TOF) values obtained herein-up to 1540 and 86 h −1 , respectively-outmatched the values reported in the literature, with FeCl2•4H2O in refluxing acetonitrile (TON ≤ 9 and TOF ≤ 2.2 h −1 ) [44], or under microwave irradiation (TON ≤ 16.8 and TOF ≤ 33.6 h −1 ) [45].…”

Section: Catalytic Transformation Of Alcohols and Amines Into Amidessupporting

confidence: 87%

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

Yalymov

¹

,

Bilyachenko

²

,

Levitsky

³

et al. 2017

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“…Complex 2 was also evaluated in the formation of amides directly from alcohols and amines, in the presence of tert ‐butyl hydroperoxide as the terminal oxidant. For this purpose, we chose the newly developed metal‐catalyzed microwave‐activated amidation between benzylic alcohol and (±)‐α‐methylbenzylammonium chloride (Scheme ). The use of complex 2 allowed amide 5 to be obtained in a yield of 71 %.…”

Section: Figurementioning

confidence: 99%

Cage‐like Fe,Na‐Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

Bilyachenko

¹

,

Levitsky

²

,

Yalymov

³

et al. 2016

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A series of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage-like architectures have a unique type of molecular topology consisting of the hexairon oxo {Fe O } core surrounded in a triangular manner by three cyclic germoxanolates [PhGe(O)O] . This structural organization induces antiferromagnetic interactions between the Fe ions through the oxygen atoms. Evaluated for this first time in catalysis, these compounds showed a high catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.

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“…Complex 2 was also evaluated in the formation of amides directly from alcohols and amines, in the presence of tert ‐butyl hydroperoxide as the terminal oxidant. For this purpose, we chose the newly developed metal‐catalyzed microwave‐activated amidation between benzylic alcohol and (±)‐α‐methylbenzylammonium chloride (Scheme ). The use of complex 2 allowed amide 5 to be obtained in a yield of 71 %.…”

Section: Figurementioning

confidence: 99%

Cage‐like Fe,Na‐Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

Bilyachenko

¹

,

Levitsky

²

,

Yalymov

³

et al. 2016

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As eries of four unprecedented heterometallic metallagermsesquioxanes were synthesized. Their cage-like architectures have au nique type of molecular topology consisting of the hexairon oxo{ Fe 6 O 19 }c ore surrounded in at riangular manner by three cyclic germoxanolates [PhGe-(O)O] 5 .T his structural organization induces antiferromagnetic interactions between the Fe III ions through the oxygen atoms.E valuated for this first time in catalysis,t hese compounds showed ah igh catalytic activity in the oxidation of alkanes and the oxidative formation of benzamides from alcohols.The design of metal-based polycyclicc age-like compounds has attracted ag reat deal of attention from researchers worldwide over several decades owing to their structural diversity and their potential technological applications especially in catalysis. [1] Numerous metal-oxygen clusters, [1b,c,j] metal-organic frameworks [1d,l,m] or metal-organic polyhedrons [1f,n] have been designed by using av ariety of selfassembling or templated reactions.A mong those,awide family of polynuclear cage-like metallasilsesquioxanes (CLMSs) architectures with interesting structural topologies [2] and important catalytic activity (e.g.i ne poxidation, oxidation and polymerization) [3] has been synthesized through ar eaction involving transition-metal ions and silsesquioxane [RSiO 1.5 ] n ligands.S urprisingly,e xamples of cage-like architectures involving another metalloid close to silicon, namely germanium, are scarce despite the great potential of this element in organometallic chemistry.T oour knowledge there is only aseries of compounds obtained from germasesquioxane [RGeO 1.5 ] 2 (R = HOOCCH 2 CH 2 )and various cations. [4] Their hydrothermal synthesis requires relatively hard conditions consisting of several days of reactions at 110 8 8C. It is worth mentioning that to date focus has only been on the synthesis,t hermogravimetric analysis,l uminescence, and sorption properties of these architectures and no investigation of the catalytic activity of metallagermanates has been reported.Herein, we report an alternative and simplified synthetic approach to design aseries of unprecedented individual cagelike metallagermsesquioxanes under mild conditions.I n addition, the catalytic activity and magnetic properties of the metallagermsesquioxanes will be discussed.Thes ingle crystals of Fe,Na-phenylgermsesquioxane [(Ph 5 Ge 5 O 10 ) 3 Fe 6 (OH) 3 (O)Na 2 ]·(EtOH) 2 ·H 2 O 1 (10 %y ield) were obtained by ar eaction between phenyltrimethoxygermane PhGe(OMe) 3 ,N aOH and anhydrous FeCl 3 in ethanol with further crystallization. Thea ddition of N-containing ligands,s uch as phenanthroline,b ipyridine,o rn eocuproine to this reaction allowed us to isolate complexes

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Iron/Caffeine as a Catalytic System for Microwave‐Promoted Benzamide Formation

Cited by 23 publications

References 43 publications

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

Cage‐like Fe,Na‐Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

Cage‐like Fe,Na‐Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

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