Organocatalytic Enantioselective 1,12-Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ

Wang, Xing1; Shen, Boming2; Liu, Meiwen2; Wang, Ziyang1; Liu, Chang2; Li, Pengfei2; Yu, Peiyuan2; Li, Wenjun1

2024-07-15

10.1002/anie.202400143

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

["The chemistry of quinone methides formed in situ has been flourishing in recent years. In sharp contrast, the development and utilization of biphenyl quinone methides are rare. In this study, we achieved a remote stereocontrolled 1,12-conjugate addition of biphenyl quinone methides formed in situ for the first time. In the presence of a suitable chiral phosphoric acid, alkynyl biphenyl quinone methides were generated from alpha-[4-(4-hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective 1,12-conjugate addition with indole-2-carboxylates. The strategy enabled the alcohols to serve as efficient allenylation reagents, providing practical access to a broad range of axially chiral allenes bearing a (1,1 '-biphenyl)-4-ol unit, which were previously less accessible. Combined with control experiments, density functional theory calculations shed light on the reaction mechanism, indicating that enantioselectivity originates from the nucleophilic addition of alkynyl biphenyl quinone methides. Notably, not only the presence of biphenyl quinone methides as versatile intermediates was confirmed but also organocatalytic enantioselective 1,12-addition was established.","Chiral phosphoric acid catalyzed 1,12-addition of indole-2-carboxylates to alkynyl biphenyl quinone methides formed in situ from alpha-[4-(4-hydroxyphenyl)phenyl]propargyl alcohols furnished a wide range of axially chiral tetrasubstituted allenes in high yields with good enantioselectivity. image"]

1,12-addition axial chiral allenes chiral phosphoric acids biphenyl quinone methides propargyl alcohols

SCI ; EI

英语

通讯

Natural Science Foundation of Shandong Province[ZR2021MB026] ; Guangdong Innovative Program[2019BT02Y335] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; National Natural Science Foundation of China[22171130] ; null[tsqn201812047]

Chemistry

Chemistry, Multidisciplinary

WOS:001247262200001

WILEY-V C H VERLAG GMBH

20242416260637

Addition reactions ; Carboxylation ; Density functional theory ; Enantioselectivity ; Hydrocarbons ; Stereochemistry

Chemistry:801 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

CHEMISTRY

Web of Science

1.Qingdao Univ, Sch Pharm, Dept Med Chem, Qingdao 266021, Shandong, Peoples R China
2.Southern Univ Sci & Technol SUSTech, Guangming Adv Res Inst, Coll Sci, Guangdong Prov Key Lab Catalysis,Dept Chem, Shenzhen 518055, Peoples R China

Wang, Xing,Shen, Boming,Liu, Meiwen,et al. Organocatalytic Enantioselective 1,12-Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2024,63(29).

Wang, Xing.,Shen, Boming.,Liu, Meiwen.,Wang, Ziyang.,Liu, Chang.,...&Li, Wenjun.(2024).Organocatalytic Enantioselective 1,12-Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,63(29).

Wang, Xing,et al."Organocatalytic Enantioselective 1,12-Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 63.29(2024).