TY - JOUR
T1 - Twisted N-Acyl-hydantoins
T2 - Rotationally Inverted Urea-Imides of Relevance in N-C(O) Cross-coupling
AU - Szostak, Roman
AU - Liu, Chengwei
AU - Lalancette, Roger
AU - Szostak, Michal
N1 - Funding Information:
We gratefully acknowledge Rutgers University and the NSF (CAREER CHE-1650766) for support. The 500 MHz spectrometer was supported by the NSF-MRI grant (CHE-1229030). We thank the Wroclaw Center for Networking and Supercomputing (Grant WCSS159).
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/12/7
Y1 - 2018/12/7
N2 - We report a combined structural and computational study on the properties of twisted acyclic hydantoins. These compounds feature cyclic urea-imide moiety that is widely found in bioactive compounds and is structurally related to the classic bridged hydantoins proposed by Smissman more than 50 years ago. We demonstrate that C to N-substitution of the imide moiety in the succinimide ring to give hydantoin results in one of the most distorted acyclic amide bonds reported to date. The energetic properties of twisted acyclic hydantoins with respect to structures, resonance energies, barriers to rotation, and proton affinities are discussed. The energetic and structural properties of twisted acyclic hydantoins described provide a benchmark to facilitate the development of twisted amides based on the biorelevant cyclic urea-imide scaffold.
AB - We report a combined structural and computational study on the properties of twisted acyclic hydantoins. These compounds feature cyclic urea-imide moiety that is widely found in bioactive compounds and is structurally related to the classic bridged hydantoins proposed by Smissman more than 50 years ago. We demonstrate that C to N-substitution of the imide moiety in the succinimide ring to give hydantoin results in one of the most distorted acyclic amide bonds reported to date. The energetic properties of twisted acyclic hydantoins with respect to structures, resonance energies, barriers to rotation, and proton affinities are discussed. The energetic and structural properties of twisted acyclic hydantoins described provide a benchmark to facilitate the development of twisted amides based on the biorelevant cyclic urea-imide scaffold.
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U2 - 10.1021/acs.joc.8b02691
DO - 10.1021/acs.joc.8b02691
M3 - Article
C2 - 30352152
AN - SCOPUS:85058191261
SN - 0022-3263
VL - 83
SP - 14676
EP - 14682
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 23
ER -