Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/70897
標題: Preparation, characterization, and reactions of (EDBP)Al(mu-(OPr)-Pr-i) (2), a novel catalyst for MPV hydrogen transfer reactions
作者: Ko, B.T.
Wu, C.C.
Lin, C.C.
關鍵字: reduction;ketones;crystal;metal;reactivity;alkoxides;complexes
Project: Organometallics
期刊/報告no:: Organometallics, Volume 19, Issue 10, Page(s) 1864-1869.
摘要: 
The reaction of [(mu-EDBP)AlMe](2) (EDBP-H-2 = 2,2'-ethylidenebis(4,6-di-tert-butylphenol) with 2 mol equiv of 2-propanol at ambient temperature yields [(EDBP)Al(mu-(OPr)-Pr-i)](2) (1), which has shown excellent catalytic activities toward hydrogen transfer reactions between aldehydes and 2-propanol (Meerwein-Ponndorf-Verley (MPV) reactions). The addition of 4 mol equiv of benzaldehyde, 4-methoxybenzaldehyde, or 4-chlorobenzaldehyde to [(EDBP)Al(mu-(OPr)-Pr-i)](2) yields [(EDBP)Al(mu-OBz-p-X)(O=CHC6H4-p-X)](2) (2, X = H; 3, X = OMe; 4, X = Cl). However, in the reaction of 1 with excess 4-nitrobenzaldehyde, only the four-coordinated complex [(EDBP)Al(mu-OBz-p-NO2)](2) (5) was obtained. Complex 1 further reacts with 2 mol equiv of OPPh3 or hexamethylphosphoramide (HMPA), yielding the four-coordinated monomeric complex [(EDBP)Al((OPr)-Pr-i)(S)] (6, S = OPPh3; 7, S = HMPA). Compounds 1, 3, 6, and 7 have been characterized by X-ray crystal structure determinations, enabling us to describe the intermediate of the MPV reactions.
URI: http://hdl.handle.net/11455/70897
ISSN: 0276-7333
DOI: 10.1021/om9909690
Appears in Collections:期刊論文

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