Unveiling the Structural Complexity of Lithium Organozinc Alkoxo Clusters and their Applications to Enantioselective Michael Addition Reactions DOI Creative Commons
Marzia Dell’Aera, Filippo Maria Perna, Paola Vitale

et al.

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(34)

Published: Sept. 23, 2024

Abstract We report three novel lithium zincate alkoxo clusters, which can be accessed through a convenient co‐complexation reaction of the corresponding dialkylzinc derivatives with alkoxides formula [LiO(CH 2 ) N(CH 3 ], or via deprotonation process mediated by higher‐order Li ZnEt 4 and dimethylethanolamine. These complexes have been isolated as colourless crystalline solids characterised multinuclear magnetic resonance spectroscopy, elemental single‐crystal X‐ray diffraction analysis. XRD analysis crystal structures, combined 1 H DOSY NMR experiments, was crucial for understanding chemistry behind these complexes. Furthermore, obtained mixing chiral nonracemic alkoxide generated from (1 R ,2 S )‐ N ‐methylephedrine explored in promoting an enantioselective Michael addition towards trans ‐β‐nitrostyrene, nitroalkane up to 37.3 % enantiomeric excess.

Language: Английский

Synthesis and Modular Reactivity of Low Valent Al/Zn Heterobimetallics Supported by Common Monodentate Amides DOI Creative Commons
Fabian Dankert, Eva Hevia

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(16)

Published: Jan. 8, 2024

Abstract Recent advances on low valent main group metal chemistry have shown the excellent potential of heterobimetallic complexes derived from Al(I) to promote cooperative small molecule activation processes. A signature feature these is use bulky chelating ligands which act as spectators providing kinetic stabilization their highly reactive Al−M bonds. Here we report synthesis novel Al/Zn bimetallics prepared by selective formal insertion AlCp* into Zn−N bond utility zinc amides ZnR 2 (R=HMDS, hexamethyldisilazide; or TMP, 2,2,6,6‐tetramethylpiperidide). By systematically assessing reactivity new [(R)(Cp*)AlZn(R)] towards carbodiimides, structural and mechanistic insights been gained ability undergo in Zn−Al bond. Disclosing a ligand effect, when R=TMP, an isomerization process can be induced giving [(TMP) AlZn(Cp*)] displays special carbodiimides carbon dioxide involving both its Al−N bonds, leaving Al−Zn untouched.

Language: Английский

Citations

2
Unveiling the Structural Complexity of Lithium Organozinc Alkoxo Clusters and their Applications to Enantioselective Michael Addition Reactions DOI Creative Commons
Marzia Dell’Aera, Filippo Maria Perna, Paola Vitale

et al.

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(34)

Published: Sept. 23, 2024

Abstract We report three novel lithium zincate alkoxo clusters, which can be accessed through a convenient co‐complexation reaction of the corresponding dialkylzinc derivatives with alkoxides formula [LiO(CH 2 ) N(CH 3 ], or via deprotonation process mediated by higher‐order Li ZnEt 4 and dimethylethanolamine. These complexes have been isolated as colourless crystalline solids characterised multinuclear magnetic resonance spectroscopy, elemental single‐crystal X‐ray diffraction analysis. XRD analysis crystal structures, combined 1 H DOSY NMR experiments, was crucial for understanding chemistry behind these complexes. Furthermore, obtained mixing chiral nonracemic alkoxide generated from (1 R ,2 S )‐ N ‐methylephedrine explored in promoting an enantioselective Michael addition towards trans ‐β‐nitrostyrene, nitroalkane up to 37.3 % enantiomeric excess.

Language: Английский

Citations

1