Organoaluminum cations for carbonyl activation

Kannan, Ramkumar; Chambenahalli, Raju; Kumar, Sandeep; Krishna, Athul; Andrews, Alex P.; Jemmis, Eluvathingal D.; Venugopal, Ajay

doi:10.1039/c9cc08272g

Cited by 30 publications

(23 citation statements)

References 65 publications

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“…Our observations on benzaldehyde and acetophenone hydrosilylation with the dicationic bismuth catalyst contrasts the findings with B(C 6 F 5 ) 3 , which is proposed to proceed by Si−H coordination to the boron center . Hence, we speculate a C=O activation hydrosilylation pathway …”

Section: Methodscontrasting

confidence: 99%

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Kannan

Balasubramaniam

Kumar

et al. 2020

Chemistry A European J

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Bismuth compounds are gaining importancea s potential alternatives to transition-metal complexes and electrond eficient lighter p-block compounds in homogeneous catalysis. Computationalanalysiso nt he two-coordinate [(Me 2 NC 6 H 4)Bi] 2 + possessing three electrophilics ites is experimentally evidencedb yt he isolation of [{Me 2 NC 6 H 4 }Bi{OP(NMe 2) 3 } 3 ][B(3,5-C 6 H 3 Cl 2) 4 ] 2 .T hese observationsl ed us to generate dicationic organobismuth catalyst, [(Me 2 NC 6 H 4)Bi(L) 3 ] 2 + (L = aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal Xray diffraction in the solids tate. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support ac arbonyl activation mechanism at the bismuth center followed by SiÀHa ddition. Scheme1.Synthetic route for the preparation of 1-3 and generation of the active catalyst in CH 2 Cl 2 .

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Section: Methodscontrasting

confidence: 99%

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Kannan

Balasubramaniam

Kumar

et al. 2020

Chemistry A European J

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“…This transformation, known as the Tishchenko reaction, is traditionally catalysed by Al alkoxides [45–47] . The ability of cationic Al complexes to mediate this reaction was demonstrated by the group of Venugopal just recently [48] …”

Section: Catalytic Imine Hydrogenationmentioning

confidence: 99%

“…[45][46][47] The ability of cationic Al complexes to mediate this reaction was demonstrated by the group of Venugopal just recently. [48]…”

Section: Catalytic Imine Hydrogenationmentioning

confidence: 99%

Cationic Aluminium Complexes as Catalysts for Imine Hydrogenation

Friedrich

Eyselein

Elsen

et al. 2021

Chemistry A European J

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Strongly Lewis acidic cationic aluminium complexes, stabilized by β–diketiminate (BDI) ligands and free of Lewis bases, have been prepared as their B(C6F5)4− salts and were investigated for catalytic activity in imine hydrogenation. The backbone (R1) and N (R2) substituents on the R1,R2BDI ligand (R1,R2BDI=HC[C(R1)N(R2)]2) influence sterics and Lewis acidity. Ligand bulk increases along the row Me,DIPPBDI

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“…All other reported main group catalysts exhibit TOF in the range of 1-2000 h À 1 for benzophenone hydroboration. [26][27][28][29][30] Results from the hydroboration of dialkyl ketones were found to be remarkable. Under solvent-free conditions, TOFs of 57,000 h À 1 , 58,200 h À 1 , 59,400 h À 1 were noticed for 2-pentanone, 1,3-dichloroacetone, and cyclohexanone, respectively (See Scheme 4, a, d and e).…”

Section: Resultsmentioning

confidence: 99%

[(Me₆TREN)MgOCHPh₂][B(C₆F₅)₄]: A Model Complex to Explore the Catalytic Activity of Magnesium Alkoxides in Ketone Hydroboration

et al. 2021

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The sterically hindered monomeric alkoxomagnesium compound [(Me 6 TREN)MgOCHPh 2 ][B(C 6 F 5 ) 4 ] (1) has been used to explore the role of magnesium alkoxides in ketone hydroboration. Experiments and DFT calculations are suggestive of a concerted reaction pathway traversing through a six-membered transition state involving MgÀ OCHPh 2 , BÀ H, and C=O bonds. Prompted by this hypothesis, we investigated the activity of [Mg(OCHPh 2 ) 2 ] (3), which exhibits turn-over frequency reaching up to 59,400 h À 1 under solvent-free conditions and stability towards C=C, À OH, À NH 2 and À NO 2 . Due to the non-existence of a metal hydride intermediate, such catalytic reactions will not get hindered in the presence of additional reactive functional groups.

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Organoaluminum cations for carbonyl activation

Abstract: A Lewis acidic cationic organoaluminum catalyst is demonstrated to perform aldehyde dimerization and ketone hydrosilylation via a carbonyl activation pathway.

Cited by 30 publications

References 65 publications

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Cationic Aluminium Complexes as Catalysts for Imine Hydrogenation

[(Me₆TREN)MgOCHPh₂][B(C₆F₅)₄]: A Model Complex to Explore the Catalytic Activity of Magnesium Alkoxides in Ketone Hydroboration

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Organoaluminum cations for carbonyl activation

Abstract: A Lewis acidic cationic organoaluminum catalyst is demonstrated to perform aldehyde dimerization and ketone hydrosilylation via a carbonyl activation pathway.

Cited by 30 publications

References 65 publications

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Cationic Aluminium Complexes as Catalysts for Imine Hydrogenation

[(Me6TREN)MgOCHPh2][B(C6F5)4]: A Model Complex to Explore the Catalytic Activity of Magnesium Alkoxides in Ketone Hydroboration

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[(Me₆TREN)MgOCHPh₂][B(C₆F₅)₄]: A Model Complex to Explore the Catalytic Activity of Magnesium Alkoxides in Ketone Hydroboration