Preparation of (2S)- and (2R)-8-prenylnaringenin, used in e.g. pharmaceuticals, comprises reducing racemic mixture of 8-prenylnarignenin derivative with formic acid and base, separating non-transferred enantiomer and splitting acyl residue

摘要

Preparation of (2S)- and (2R)-8-prenylnaringenin comprises reducing a racemic mixture of 8-prenylnarignenin derivative (rac-1) with a mixture of formic acid and a base in the presence of chiral catalyst (2) comprising a central metal (M) such as rhodium (III), ruthenium (II) or iridium (III), separating the non-transferred enantiomer (2S)-1 or (2R)-1 of the reduced product and splitting the acyl residue R1 and R2 in (2S)-1 or (2-R) by enzyme catalyst solvolysis to (2S)-8-prenylaringenin (Ia) or (2R)-8-prenylaringenin (Ib). Preparation of (2S)- and (2R)-8-prenylnaringenin comprises reducing a racemic mixture of 8-prenylnarignenin derivative of formula (rac-1) with a mixture of formic acid and a base in the presence of chiral catalyst of formula (2) comprising a central metal (M) such as rhodium(III), ruthenium(II) or iridium(III), a pi -ligand A of formula (3) or (4), a chiral diamine-ligand (5) of formula (CH(R1a>)(NH-R4>)-CH(R2a>)(N)-S(O)2-R3a>) , a ligand B such as hydrogen, chloride or other suitable anion, separating the non-transferred enantiomer (2S)-1 or (2R)-1 of the reduced product and splitting the acyl residue R1 and R2 in (2S)-1 or (2-R) by enzyme catalyst solvolysis to (2S)-8-prenylaringenin of formula (Ia) or (2R)-8-prenylaringenin of formula (Ib). In the catalyst, when the chiral diamine ligand is (R,R)-diamine ligand, it produces prenylnaringenine compound of formula (2S)-1 or (2R, 4R)-2 and when it is (S,S)-diamine ligand, it produces prenylaringenine compound of formula (2R)-1 or (2S, 4S)-2. R1>, R2> = acyl; M = rhodium (III), ruthenium (II) or iridium (III); R5>, R6> = alkyl or aryl; R7>, R8> = H or alkyl; R1a>-R3a>=H or alkyl, and R4>=H or alkyl. [Image] [Image] [Image] [Image].