Ruthenium Complexes with Exclusive Octahedral Centrochirality for Asymmetric Catalysis

• Applicant: Professor Dr. Eric Leif Meggers
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2017 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 370920062

• Final Report Year: 2023

Final Report Abstract

Das Projekt hat sich mit der Entwicklung und Anwendung von neuartigen Rutheniumkatalysatoren mit ausschließlich metallzentrierter Chiralität beschäftigt. Dieses Forschungsvorhaben hat sich als ausgesprochen produktiv erwiesen. Es konnten eine ganze Reihe neuartiger chiral-at-Ru-Komplexe entwickelt und untersucht werden. Dabei zeigten einige dieser Komplexe ausgesprochen interessante katalytische Eigenschaften, insbesondere hinsichtlich von Nitren-vermittelten enantioselektiven C(sp3)−H- Funktionalisierungen. Im Rahmen dieser DFG-Förderung konnten bisher 17 Forschungspublikationen und ein Accountartikel publiziert werden.

Publications

• Arylketone π-Conjugation Controls Enantioselectivity in Asymmetric Alkynylations Catalyzed by Centrochiral Ruthenium Complexes. Journal of the American Chemical Society, 140(15), 5146-5152.
  Chen, Shuming; Zheng, Yu; Cui, Tianjiao; Meggers, Eric & Houk, K. N.
  
• Catalytic Enantioselective Intramolecular C(sp3)−H Amination of 2‐Azidoacetamides. Angewandte Chemie International Edition, 58(4), 1088-1093.
  Zhou, Zijun; Chen, Shuming; Qin, Jie; Nie, Xin; Zheng, Xingwen; Harms, Klaus; Riedel, Radostan; Houk, K. N. & Meggers, Eric
  
• Catalytic Enantioselective Synthesis of Key Propargylic Alcohol Intermediates of the Anti-HIV Drug Efavirenz. Organic Process Research & Development, 22(1), 103-107.
  Zheng, Yu; Zhang, Lilu & Meggers, Eric
  
• Chiral‐at‐Ruthenium Catalyst with Sterically Demanding Furo[3,2‐b]pyridine Ligands. European Journal of Inorganic Chemistry, 2019(2), 195-198.
  Cui, Tianjiao; Qin, Jie; Harms, Klaus & Meggers, Eric
  
• Enantioselective intramolecular C–H amination of aliphatic azides by dual ruthenium and phosphine catalysis. Chemical Science, 10(11), 3202-3207.
  Qin, Jie; Zhou, Zijun; Cui, Tianjiao; Hemming, Marcel & Meggers, Eric
  
• Non-C2-Symmetric Chiral-at-Ruthenium Catalyst for Highly Efficient Enantioselective Intramolecular C(sp3)–H Amidation. Journal of the American Chemical Society, 141(48), 19048-19057.
  Zhou, Zijun; Chen, Shuming; Hong, Yubiao; Winterling, Erik; Tan, Yuqi; Hemming, Marcel; Harms, Klaus; Houk, K. N. & Meggers, Eric
  
• Asymmetric Ring-Closing Aminooxygenation of Alkenes en Route to 2-Amino-1,3-Diols with Vicinal Stereocenters. Organic Letters, 22(16), 6653-6656.
  Tan, Yuqi; Han, Feng; Hemming, Marcel; Wang, Jie; Harms, Klaus; Xie, Xiulan & Meggers, Eric
  
• Catalytic enantioselective synthesis of β-amino alcohols by nitrene insertion. Science China Chemistry, 64(3), 452-458.
  Zhou, Zijun; Tan, Yuqi; Shen, Xiang; Ivlev, Sergei & Meggers, Eric
  
• Complementing Pyridine‐2,6‐bis(oxazoline) with Cyclometalated N‐Heterocyclic Carbene for Asymmetric Ruthenium Catalysis. Angewandte Chemie International Edition, 59(30), 12392-12395.
  Li, Long; Han, Feng; Nie, Xin; Hong, Yubiao; Ivlev, Sergei & Meggers, Eric
  
• Enantioselective Ring-Closing C–H Amination of Urea Derivatives. Chem, 6(8), 2024-2034.
  Zhou, Zijun; Tan, Yuqi; Yamahira, Tatsuya; Ivlev, Sergei; Xie, Xiulan; Riedel, Radostan; Hemming, Marcel; Kimura, Masanari & Meggers, Eric
  
• Intramolecular C(sp3)–H Bond Oxygenation by Transition‐Metal Acylnitrenoids. Angewandte Chemie International Edition, 59(48), 21706-21710.
  Tan, Yuqi; Chen, Shuming; Zhou, Zijun; Hong, Yubiao; Ivlev, Sergei; Houk, K. N. & Meggers, Eric
  
• Ruthenium Pybox-Catalyzed Enantioselective Intramolecular C–H Amination of Sulfamoyl Azides en Route to Chiral Vicinal Diamines. The Journal of Organic Chemistry, 86(1), 750-761.
  Nie, Xin; Yan, Zihan; Ivlev, Sergei & Meggers, Eric
  
• Chiral-at-Ruthenium Catalysts with Mixed Normal and Abnormal N-Heterocyclic Carbene Ligands. Organometallics, 40(8), 1148-1155.
  Winterling, Erik; Ivlev, Sergei & Meggers, Eric
  
• Deracemization of Chiral-at-Ruthenium Catalyst by Diastereoselective Dynamic Resolution. Organometallics, 41(1), 52-59.
  Baran, Dominik; Ivlev, Sergei I. & Meggers, Eric
  
• Chiral-at-Ru Catalyst with Cyclometalated Imidazo[1,5-a]pyridin­ylidene for Enantioselective Intramolecular Cyclopropanations. Synlett, 34(12), 1403-1408.
  Meggers, Eric; Han, Feng; Xie, Yuanhao; Xie, Xiulan & Ivlev, Sergei I.
  
• Cyclometalated Chiral-at-Ruthenium Catalyst for Enantioselective Ring-Closing C(sp3)–H Carbene Insertion to Access Chiral Flavanones. ACS Catalysis, 12(16), 10304-10312.
  Han, Feng; Choi, Peter H.; Ye, Chen-Xi; Grell, Yvonne; Xie, Xiulan; Ivlev, Sergei I.; Chen, Shuming & Meggers, Eric
  
• Stereocontrolled 1,3-nitrogen migration to access chiral α-amino acids. Nature Chemistry, 14(5), 566-573.
  Ye, Chen-Xi; Shen, Xiang; Chen, Shuming & Meggers, Eric
  
• Chiral-at-Ruthenium Catalysts for Nitrene-Mediated Asymmetric C–H Functionalizations. Accounts of Chemical Research, 56(9), 1128-1141.
  Ye, Chen-Xi & Meggers, Eric