ISSN:
0018-019X
Schlagwort(e):
Chemistry
;
Organic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
A systematic investigation of the rotational behavior of aryl substituents in α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanols (TADDOLs) is presented. In the use as chiral ligands for enantioselective metal-catalyzed reactions, a change from phenyl to bulkier substituents, e.g., 1-naphthyl, gives rise to an astounding alteration of the selectivity, The possible existence of preferred rotamers of TADDOLs has so far not been given due attention, which encouraged us to look at the validity of the Knowles model, originally formulated for diaryl substituted bisphosphines. 1H-NMR Investigations at various temperatures as well as X-ray powder diffraction were employed to study the rotation in the case of tetra(1-naphthyl) TADDOL 1. To support the interpretation of the experimental results, molecular mechanics, semiempirical, and ab initio calculations were performed. For comparison, the energy surface of tetraphenyl TADDOL 2 was calculated as well. Our results lead to the conclusion that for 1, only one major conformation is present in both solution and solid state, which determines the stereochemical outcome of the catalyzed reactions.
Zusätzliches Material:
7 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/hlca.19970800708
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