Catalytic Enantioselective Intramolecular C(sp3)−H Amination of 2‐Azidoacetamides
An enantioselective ring‐closing C(sp3)−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral imidazolidin‐4‐ones in 31–95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). T...
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Published in | Angewandte Chemie International Edition Vol. 58; no. 4; pp. 1088 - 1093 |
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Main Authors | , , , , , , , , |
Format | Journal Article |
Language | English |
Published |
WEINHEIM
Wiley
21.01.2019
Wiley Subscription Services, Inc |
Edition | International ed. in English |
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Online Access | Get full text |
ISSN | 1433-7851 1521-3773 1521-3773 |
DOI | 10.1002/anie.201811927 |
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Abstract | An enantioselective ring‐closing C(sp3)−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral imidazolidin‐4‐ones in 31–95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp3)−H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2‐azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π–π stacking between the substrate and the catalyst framework.
Achiral ligands, chiral catalyst: By utilizing a newly prepared chiral‐at‐metal ruthenium catalyst for chelate activation of 2‐azidoacetamides, the challenging catalytic enantioselective ring‐closing C(sp3)−H amination of these substrates was achieved in high yields and enantioselectivities. |
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AbstractList | An enantioselective ring-closing C(sp
)-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral imidazolidin-4-ones in 31-95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp
)-H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2-azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π-π stacking between the substrate and the catalyst framework. An enantioselective ring‐closing C(sp3)−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral imidazolidin‐4‐ones in 31–95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp3)−H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2‐azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π–π stacking between the substrate and the catalyst framework. An enantioselective ring-closing C(sp(3))-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral imidazolidin-4-ones in 31-95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp(3))-H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2-azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable pi-pi stacking between the substrate and the catalyst framework. An enantioselective ring-closing C(sp3 )-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral imidazolidin-4-ones in 31-95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp3 )-H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2-azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π-π stacking between the substrate and the catalyst framework.An enantioselective ring-closing C(sp3 )-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral imidazolidin-4-ones in 31-95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp3 )-H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2-azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π-π stacking between the substrate and the catalyst framework. An enantioselective ring‐closing C(sp3)−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral imidazolidin‐4‐ones in 31–95 % yield, with enantioselectivities of up to 95 % ee, and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp3)−H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2‐azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π–π stacking between the substrate and the catalyst framework. Achiral ligands, chiral catalyst: By utilizing a newly prepared chiral‐at‐metal ruthenium catalyst for chelate activation of 2‐azidoacetamides, the challenging catalytic enantioselective ring‐closing C(sp3)−H amination of these substrates was achieved in high yields and enantioselectivities. An enantioselective ring‐closing C(sp 3 )−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral imidazolidin‐4‐ones in 31–95 % yield, with enantioselectivities of up to 95 % ee , and at catalyst loadings down to 0.1 mol % (turnover number (TON)=740). To our knowledge, this is the first example of a highly enantioselective C(sp 3 )−H amination with aliphatic azides. Mechanistic experiments reveal the importance of the amide group, which presumably enables initial bidentate coordination of the 2‐azidoacetamides to the catalyst. DFT calculations show that the transition state leading to the major enantiomer features a better steric fit and favorable π–π stacking between the substrate and the catalyst framework. |
Author | Nie, Xin Riedel, Radostan Zheng, Xingwen Qin, Jie Meggers, Eric Harms, Klaus Zhou, Zijun Chen, Shuming Houk, K. N. |
Author_xml | – sequence: 1 givenname: Zijun surname: Zhou fullname: Zhou, Zijun organization: Philipps-Universität Marburg – sequence: 2 givenname: Shuming surname: Chen fullname: Chen, Shuming organization: University of California – sequence: 3 givenname: Jie surname: Qin fullname: Qin, Jie organization: Philipps-Universität Marburg – sequence: 4 givenname: Xin surname: Nie fullname: Nie, Xin organization: Philipps-Universität Marburg – sequence: 5 givenname: Xingwen surname: Zheng fullname: Zheng, Xingwen organization: Philipps-Universität Marburg – sequence: 6 givenname: Klaus surname: Harms fullname: Harms, Klaus organization: Philipps-Universität Marburg – sequence: 7 givenname: Radostan surname: Riedel fullname: Riedel, Radostan organization: Philipps-Universität Marburg – sequence: 8 givenname: K. N. surname: Houk fullname: Houk, K. N. email: houk@chem.ucla.edu organization: University of California – sequence: 9 givenname: Eric orcidid: 0000-0002-8851-7623 surname: Meggers fullname: Meggers, Eric email: meggers@chemie.uni-marburg.de organization: Philipps-Universität Marburg |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/30475437$$D View this record in MEDLINE/PubMed |
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Keywords | IMIDO COMPLEXES CYTOCHROME-P450 IRIDIUM BOND AMINATION AMIDATION asymmetric catalysis ruthenium catalysis azides chiral-at-metal complexes AZIRIDINATION CHEMISTRY amination DERIVATIVES C-H AMINATION ALKYL AZIDES |
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Snippet | An enantioselective ring‐closing C(sp3)−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral... An enantioselective ring‐closing C(sp 3 )−H amination of 2‐azidoacetamides is catalyzed by a chiral‐at‐metal ruthenium complex and provides chiral... An enantioselective ring-closing C(sp(3))-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral... An enantioselective ring-closing C(sp )-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral... An enantioselective ring-closing C(sp3 )-H amination of 2-azidoacetamides is catalyzed by a chiral-at-metal ruthenium complex and provides chiral... |
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SubjectTerms | Aliphatic compounds Amination asymmetric catalysis azides Catalysis Catalysts Chemistry Chemistry, Multidisciplinary chiral-at-metal complexes Coordination compounds Enantiomers Physical Sciences Ruthenium ruthenium catalysis Ruthenium compounds Science & Technology Substrates |
Title | Catalytic Enantioselective Intramolecular C(sp3)−H Amination of 2‐Azidoacetamides |
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