Barriers to Rotation in ortho-Substituted Tertiary Aromatic Amides: Effect of Chloro-Substitution on Resonance and Distortion

被引:31
作者
Bisz, Elwira [2 ]
Piontek, Aleksandara [2 ]
Dziuk, Blazej [2 ]
Szostak, Roman [3 ]
Szostak, Michal [1 ,2 ]
机构
[1] Opole Univ, Dept Chem, 48 Oleska St, PL-45052 Opole, Poland
[2] Univ Wroclaw, Dept Chem, F Joliot Curie 14, PL-50383 Wroclaw, Poland
[3] Rutgers State Univ, Dept Chem, 73 Warren St, Newark, NJ 07102 USA
关键词
BRIDGEHEAD BICYCLIC LACTAMS; HIGHLY TWISTED AMIDES; STEREOCHEMICAL INFORMATION; REACTIVITY; CHEMISTRY; TETRAFLUOROBORATE; DESTABILIZATION; ISOMERIZATION; COMMUNICATION; SPECTROSCOPY;
D O I
10.1021/acs.joc.8b00019
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Planarity of the amide bond represents one of the most widely recognized properties of amides. Herein, we report a combined structural and computational study on the effect of ortho-substitution on resonance and barriers to rotation in tertiary aromatic amides. We demonstrate that ortho-chloro substitution in a class of benzamides that are important from the reactivity and medicinal chemistry perspective results in increased barriers to rotation around both the N-C(O) and C-C(O) axes. The effect of steric hindrance on structures, resonance energies, barriers to rotation, and proton affinities is discussed. The present study strongly supports the use of ortho-substitution in common benzamides to strengthen amidic resonance.
引用
收藏
页码:3159 / 3163
页数:5
相关论文
共 59 条
  • [1] Thieme Chemistry Journals Awardees - Where Are They Now? Bis(2-pyridyl)amides as Readily Cleavable Amides Under Catalytic, Neutral, and Room-Temperature Conditions
    Adachi, Shinya
    Kumagai, Naoya
    Shibasaki, Masakatsu
    [J]. SYNLETT, 2018, 29 (03) : 301 - 305
  • [2] Pyramidalization/twisting of the amide functional group via remote steric congestion triggered by metal coordination
    Adachi, Shinya
    Kumagai, Naoya
    Shibasaki, Masakatsu
    [J]. CHEMICAL SCIENCE, 2017, 8 (01) : 85 - 90
  • [3] Barriers to rotation about the chiral axis of tertiary aromatic amides
    Ahmed, A
    Bragg, RA
    Clayden, J
    Lai, LW
    McCarthy, C
    Pink, JH
    Westlund, N
    Yasin, SA
    [J]. TETRAHEDRON, 1998, 54 (43) : 13277 - 13294
  • [4] [Anonymous], 2013, SCI SYNTHESIS CROSS
  • [5] Twisted Amide Analogues of Troger's Base
    Artacho, Josep
    Ascic, Erhad
    Rantanen, Toni
    Karlsson, Josefine
    Wallentin, Carl-Johan
    Wang, Ruiyao
    Wendt, Ola F.
    Harmata, Michael
    Snieckus, Victor
    Warnmark, Kenneth
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2012, 18 (04) : 1038 - 1042
  • [6] A New Twist on Amide Solvolysis
    Aube, Jeffrey
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (13) : 3063 - 3065
  • [7] Spontaneous transfer of chirality in an atropisomerically enriched two-axis system
    Barrett, Kimberly T.
    Metrano, Anthony J.
    Rablen, Paul R.
    Miller, Scott J.
    [J]. NATURE, 2014, 509 (7498) : 71 - 75
  • [8] Ultra-remote stereocontrol by conformational communication of information along a carbon chain
    Clayden, J
    Lund, A
    Vallverdú, LS
    Helliwell, M
    [J]. NATURE, 2004, 431 (7011) : 966 - 971
  • [9] Clayden J, 2002, EUR J ORG CHEM, V2002, P3558
  • [10] The twisted amide 2-quinuclidone: 60 Years in the making
    Clayden, Jonathan
    Moran, Wesley J.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (43) : 7118 - 7120