Studies on the Asymmetric Total Synthesis of d-Biotin(Ⅴ)

Abstract

Abstract: An efficient, high yielding and stereoselective synthesis of d biotin(6) is described. The stereoselective reduction of the known(3a S, 6a R)-1,3-dibenzyl tetrahydro 4Hthieno imidazol-2,4(1H)-dione(1) with diisobutylaluminum hydride(DIBAL-H) in toluene gave(3a S, 4 S, 6a R)-1,3 dibenzyl-4-hydroxy tetrahydro 1Hthieno imidazol-2(3H)-one(2) in 91% yield with 99.7% e.e.. Alcohol 2 was directly converted into(3a S, 4 S, 6a R) phosphonium salt 3 upon reaction with triphenylphosphine hydrogen tetrafluoroborate. Condensation of the corresponding ylide with 4 formylbutric acid afforded unsaturated acid 4. Catalytic hydrogen transfer hydrogenation of compound 4 with Pd D297 resin/ammonium formate system led stereoselectively to(3a S, 4 S, 6a S)-dibenzylbiotion(5), which was debenzylated by treatment with orthophospaoric acid in the presence of phenol to yield d biotin(6). The overall yield of d biotin was 42% from thiolactone 1.

Key words: d Biotin, Vitamin H, Steroselective reduction, Catalytic hydrogen transfer, Asymmetric synthesis

CLC Number:

R914.5

TrendMD:

CHEN Fen-Er, FU Han, MENG Ge, LUO You-Fu, YAN Ming-Guo . Studies on the Asymmetric Total Synthesis of d-Biotin(Ⅴ)[J]. Chem. J. Chinese Universities, 2002, 23(6): 1060.

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Studies on the Asymmetric Total Synthesis of d-Biotin(Ⅴ)

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