환상 α,β-불포화 카르보닐 화합물의 선택적 에폭시화 및 환원

Selective Epoxidation and Reduction of Rigid Cyclic α,β-Unsaturated Carbonyl Compounds

Diosgenin (25(R)-spirost-5-en-3 β-ol) was oxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form 25(R)-1,4,6-spirostatrien-3-one (1) as rigid cyclic α,β-unsaturated carbonyl compound. This compound was reacted with H2O2, m-chloroperoxybenzoic acid (mCPBA), NaOCl in the presence with (R,R)- or (S,S)-Jacobsen catalyst, tert-butyl-hydroperoxide (TBHP) in Mo(CO)6, and in VO(acac)2 catalyst, respectively. 25(R)-1,4,6-spirostatrien-3-one (1) was reduced with NaBH4, L-Selectride, LiAIH4, BH3(CH3)2S, Superhydride, Red-Al, and lithium tri-tert-butoxyaluminium hydride. And 25(R)-4,6-spirostadien-3β-ol (4) was treated with H2O2, mCPBA, TBHP in D-(-)- and L-(+)-diisopropyltar-trate and Ti(O-iPr)4 condition (Sharpless asymmetric epoxidation), TBHP in Mo(CO)6 and in VO(acac)2 catalyst, respectively.