Zirconocene-Initiated Intramolecular Hydride Transfer in N-Iso­alkyl-Substituted Propargylamines

Ilfir Ramazanov; Rita Kadikova; Zukhra Saitova; Usein Dzhemilev

doi:10.1055/s-0037-1609336

Zirconocene-Initiated Intramolecular Hydride Transfer in N-Isoalkyl-Substituted Propargylamines

Synlett ◽

10.1055/s-0037-1609336 ◽

2018 ◽

Vol 29 (09) ◽

pp. 1191-1194

Author(s):

Ilfir Ramazanov ◽

Rita Kadikova ◽

Zukhra Saitova ◽

Usein Dzhemilev

Keyword(s):

Hydride Transfer ◽

Organoaluminum Compounds ◽

Unusual Transformation

The unusual transformation of N-isoalkyl-substituted propargylamines into alkenylamines under the action of Cp2ZrCl2 and organoaluminum compounds (Me3Al, EtAlCl2) has been observed. The proposed mechanism, involving the N-isoalkyl-substituted propargylamine undergoing zirconocene-initiated intramolecular hydride transfer was supported by B3LYP/6-31G(d)/LanL2DZ calculations.

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Faculty Opinions recommendation of Quantum dynamics of hydride transfer catalyzed by bimetallic electrophilic catalysis: synchronous motion of Mg(2+) and H(-) in xylose isomerase.

Faculty Opinions – Post-Publication Peer Review of the Biomedical Literature ◽

10.3410/f.1007975.100509 ◽

2002 ◽

Author(s):

Mark Nelson

Keyword(s):

Quantum Dynamics ◽

Hydride Transfer ◽

Xylose Isomerase ◽

Synchronous Motion

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Faculty Opinions recommendation of Barriers to Hydride Transfer in Wild Type and Mutant Dihydrofolate Reductase from E. coli.

Faculty Opinions – Post-Publication Peer Review of the Biomedical Literature ◽

10.3410/f.1016691.201160 ◽

2003 ◽

Author(s):

Arieh Warshel

Keyword(s):

Dihydrofolate Reductase ◽

Hydride Transfer ◽

Wild Type ◽

E Coli

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Faculty Opinions recommendation of Lactate Racemase Nickel-Pincer Cofactor Operates by a Proton-Coupled Hydride Transfer Mechanism.

Faculty Opinions – Post-Publication Peer Review of the Biomedical Literature ◽

10.3410/f.732770883.793543614 ◽

2018 ◽

Author(s):

Michael Maroney

Keyword(s):

Hydride Transfer ◽

Transfer Mechanism

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Hydride transfer stereospecificity of rat liver aldehyde dehydrogenases.

Journal of Biological Chemistry ◽

10.1016/s0021-9258(18)60901-9 ◽

1987 ◽

Vol 262 (23) ◽

pp. 10911-10913

Author(s):

K H Jones ◽

R Lindahl ◽

D C Baker ◽

R Timkovich

Keyword(s):

Rat Liver ◽

Hydride Transfer ◽

Aldehyde Dehydrogenases

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Catalytic Systems Based on Cp2ZrX2 (X = Cl, H), Organoaluminum Compounds and Perfluorophenylboranes: Role of Zr,Zr- and Zr,Al-Hydride Intermediates in Alkene Dimerization and Oligomerization

Catalysts ◽

10.3390/catal11010039 ◽

2020 ◽

Vol 11 (1) ◽

pp. 39

Author(s):

Lyudmila V. Parfenova ◽

Pavel V. Kovyazin ◽

Almira Kh. Bikmeeva ◽

Eldar R. Palatov

Keyword(s):

Diffusion Coefficients ◽

Organoaluminum Compounds ◽

Zirconium Hydride ◽

Nmr Studies ◽

Catalytic Systems ◽

Selective Formation

The activity and chemoselectivity of the Cp2ZrCl2-XAlBui2 (X = H, Bui) and [Cp2ZrH2]2-ClAlEt2 catalytic systems activated by (Ph3C)[B(C6F5)4] or B(C6F5)3 were studied in reactions with 1-hexene. The activation of the systems by B(C6F5)3 resulted in the selective formation of head-to-tail alkene dimers in up to 93% yields. NMR studies of the reactions of Zr complexes with organoaluminum compounds (OACs) and boron activators showed the formation of Zr,Zr- and Zr,Al-hydride intermediates, for which diffusion coefficients, hydrodynamic radii, and volumes were estimated using the diffusion ordered spectroscopy DOSY. Bis-zirconium hydride clusters of type x[Cp2ZrH2∙Cp2ZrHCl∙ClAlR2]∙yRnAl(C6F5)3−n were found to be the key intermediates of alkene dimerization, whereas cationic Zr,Al-hydrides led to the formation of oligomers.

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