The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, ...The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most ofthe reported methodologies required noble transition-metals. Herein we reported the first highly asymmetricstereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylicsiloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 withP-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities(>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studieswere investigated first time by React-IR and DFT calculations to understand and explain the ligand-control ofexcellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reactiondesign was proposed for further application of this type of catalysis.展开更多
基金financial support provided by the National Natural Science Foundation of China(No.22061032)Natural Science Foundation of Inner Mongolia(Nos.2020MS02022,and 2022QN02005)+5 种基金Science and Technology Program of Inner Mongolia(No.2020GG0134)Opening-fund from State Key Laboratory of Bio-organic and Natural Products Chemistry of SIOC(No.21300-5206002)“JUN-MA”Highlevel Talents Program of Inner Mongolia University(No.21300-5185121)“Grassland Talents”Program of Inner Mongolia(No.12000-12102414)High-level Recruit Program of Inner Mongolia(No.12000-13000603)Key Project at Central Government Level:the ability establishment of sustainable use for valuable Chinese medicine resources(No.2060302)is sincerely acknowledged。
文摘The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most ofthe reported methodologies required noble transition-metals. Herein we reported the first highly asymmetricstereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylicsiloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 withP-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities(>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studieswere investigated first time by React-IR and DFT calculations to understand and explain the ligand-control ofexcellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reactiondesign was proposed for further application of this type of catalysis.
