期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 4, 页码 1035-1040出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201811517
关键词
aromatic substitution; chiral auxiliaries; chirality; noncovalent interactions; nitration
资金
- National Science Foundation [CHE-1609137]
- ACS Petroleum Research Fund [58219-DNI6]
- National Institutes of Health [S10-OD018126, P30-GM118228]
Enantioselective electrophilic aromatic nitration methodology is needed to advance chirality-assisted synthesis (CAS). Reported here is an enantioselective aromatic nitration strategy operating with chiral diester auxiliaries, and it provides an enantioselective synthesis of a C-3v-symmetric tribenzotriquinacene (TBTQ). These axially-chiral structures are much sought-after building blocks for CAS, but they were not accessible prior to this work in enantioenriched form without resolution of enantiomers. This nitration strategy controls the stereochemistry of threefold nitration reactions from above the aromatic rings with chiral diester arms. Dicarbonyl-to-arenium chelation rigidifies the reaction systems, so that remote stereocenters position the ester-directing groups selectively over specific atoms of the TBTQ framework. Closely guided by computational design, a more selective through-space directing arm was first predicted with density functional theory (DFT), and then confirmed in the laboratory, to outperform the initial structural design. This enantio- and regioselective TBTQ synthesis opens a new pathway to access building blocks for CAS.
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