羟基位于脂环→环扩大或缩小 OH H2SO4/Et2O OH rt2h O Ph ph PhPh 99%
羟基位于脂环→环扩大或缩小 OH C OH Ph Ph H2 SO4/Et 2 O r.t.2h O Ph Ph 99%
OH H3c 3 3 H3C H3c OH rans 二醇 C CH3 CH3C H3C OH
Trans-二醇 OH H3 C H3 C OH H OH2 H3 C H3 C OH H3 C OH H3 C H CH3 CH3 C O
3 Semipinacol重排 RR RR RC-C-R RC-C-R OH OH R RC-C-R NH2 O R Y为—X -OSO2R
3.Semipinacol重排 NH2 X OSO2 R Y为 R C C R R O R R C C R R R OH Y R C C R R R OHY
OSO2Ar HO t-BuOK H H3C CH3 CH3 CH 3 H3C CH3 碱性介质 仲醇选择性
• 碱性介质 • 仲醇选择性 OSO2 Ar CH3 HO H CH3 H3 C t BuOK H O H CH3 H3 C CH3
OH NH2 Nano2/HOAc CH3O C—CHPh Ph CH3O C--CL-Ph Ph 97% OH Br AgnO3/EtOH C C—CH-Ph rt Ph Ph C C-CH ph 65-78%
97% 65-78% Cl C CH O Ph Ph AgNO3/EtOH Cl C CH Ph OH Br Ph CH3 O C CH O Ph Ph NaNO2/HOAc CH3 O C CH Ph OH NH2 Ph r.t