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- Title
Enantioselektive Reaktionen an porphinoiden Nickelkomplexen.
- Authors
Meier, Kurt; Scheffold, Rolf
- Abstract
Enantioselective Reactions on Porphine Type Nickel Complexes The thermodynamically controlled addition of alcohols to (+)-(1 R)-[1-methyl-8H-HDP]nickelperchlorate ( 1; e.e. 92%) yields exclusively the corresponding cis-1,11-disubstituted porphinoids. Chemical transformation of functional groups in the alkoxy side-chain of the chiral addition product followed by acid catalyzed elimination yields the derived alcohols and 1. By this procedure, the following enantioselective transformations were studied: methylation of meso-2,3-butandiol ( 5) to (+)-(2 R,3 S)-3-methoxy-2-butanol ( 8a; e.e. 87%), diimide reduction of 2-ethylallyl alcohol ( 9) to (+)-(2 R)-2-methyl-1-butanol ( 12a; e.e. 15%), and hydride reduction of 4-hydroxy-2-butanone ( 13) to (+)-(3 S)-1,3-butandiol ( 16a; e.e. 20%). Addition of 2,2-dimethyl-1,3-propandiol ( 17) to 4, followed by esterification of the free hydroxy group with trifluoromethanesulfonic anhydride and solvolysis of the sulfonate 19 yielded a bridged complex with unrearranged alkyl chain for which structure 20 is proposed.
- Publication
Helvetica Chimica Acta, 1981, Vol 64, Issue 5, p1505
- ISSN
0018-019X
- Publication type
Article
- DOI
10.1002/hlca.19810640526