Synthese optisch aktiver Nickel‐Komplexe mit porphinoidem Ligandsystem

Synthesis of Optically Active Porphine‐type Nickel Complexes Both enantiomers of [1‐methyl‐8 H‐HDP]nickel‐perchlorate For nomenclature see footnote 5 in this paper. ( 2a and 2b , respectively) have been synthesized by the following reaction sequence: (a) base induced addition of (−)‐( R )‐2‐octanol to 1 , (b) separation of the two diastereomeric monoadducts 4a and 4b , (c) reaction with methyl magnesium iodide containing an excess of methyl iodide, (d) acid induced elimination of 2‐octanol from the diadducts 6a and 6b . By a similar procedure both enantiomers of [1‐butyl‐8 H‐HDP] nickel‐perchlorate ( 3a and 3b , respectively) have been prepared. The reaction of 3a with butyl lithium yields in a kinetically controlled addition predominantly the optically active cis ‐1, 11‐dibutyl adduct 8 and in minor quantity the meso ‐ cis ‐1, 11‐dibutyl adduct 9 .