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
Two remarkable reducing agents NaBH4 (or NaBD4)/SnCl2(or SnCl4·2Et2O) with chiral ligands are applied to the asymmetric reduction of carbonyl compounds with excellent chemical yields and enantioselective excesses.
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.
基金Project supported by the Major State Basic Research Development Program(No.G2000048007),the National Natural Science Foundation of China(No.D20032010)and Shanghai Natural Science Council.
文摘Two remarkable reducing agents NaBH4 (or NaBD4)/SnCl2(or SnCl4·2Et2O) with chiral ligands are applied to the asymmetric reduction of carbonyl compounds with excellent chemical yields and enantioselective excesses.
