CAJ | 학술논문

通过手性二胺配体与Cu或Ni络合合成了手性金属催化剂,并将其应用于α-酮酸酯对硝基烯的不对称共轭加成反应中,发展了通过改变中心金属或调节配体刚性实现反应对映选择性反转的策略。使用同一手性二胺配体(1S,1'S)-1,1'-联异吲哚啉,与不同的金属前体(Cu(OAc)2·H2O与Ni(OAc)2·4H2O)络合,可以高选择性地得到绝对构型相反的共轭加成产物(ee值高达94%与93%)。同样,使用同一金属前体Cu(OAc)2·H2O,与同一手性源出发合成的两种刚性不同的二胺配体络合,也可以在这个反应中实现产物绝对构型的反转(ee值高达94%与94%)。
통과수성이알배체여Cu혹Ni락합합성료수성금속최화제,병장기응용우α-동산지대초기희적불대칭공액가성반응중,발전료통과개변중심금속혹조절배체강성실현반응대영선택성반전적책략。사용동일수성이알배체(1S,1'S)-1,1'-련이신타람,여불동적금속전체(Cu(OAc)2·H2O여Ni(OAc)2·4H2O)락합,가이고선택성지득도절대구형상반적공액가성산물(ee치고체94%여93%)。동양,사용동일금속전체Cu(OAc)2·H2O,여동일수성원출발합성적량충강성불동적이알배체락합,야가이재저개반응중실현산물절대구형적반전(ee치고체94%여94%)。
A series of efficient catalytic systems has been developed to control the dual enantioselectivity of the conjugate addition ofα‐keto esters to nitroalkenes. The use of the chiral diamine (1S,1'S)‐1,1'‐biisoindoline as a chiral ligand with either (Cu(OAc)2·H2O or Ni(OAc)2·4H2O as the catalyst provide facile access to the respective enantiomers resulting from the conjugate addition reaction with high levels of enantioselectivity (94%ee vs 93%ee). Furthermore, the use of Cu(OAc)2·H2O as the metal center allowed the enantioselectivity of the conjugate addition reaction to be switched through the tuning of the rigidity of the chiral diamine ligand (94%ee vs 94%ee).