State Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering , Lanzhou University , Lanzhou , P.R. China.
Department of Chemistry and Center of Novel Functional Molecules , The Chinese University of Hong Kong , Shatin , Hong Kong SAR.
J Org Chem. 2018 Apr 6;83(7):3433-3440. doi: 10.1021/acs.joc.8b00375. Epub 2018 Mar 27.
A new chiral tribenzotriquinacene bearing an ortho-bromoaniline nucleus was synthesized and optically resolved. The individual enantiomers, the absolute configuration of which was confirmed by single-crystal X-ray structure analysis, were stereoselectively converted into the same pyrazine-fused syn-bis-TBTQ derivative by chirality-assisted Buchwald-Hartwig amination. The corresponding diastereomeric anti-dimer was obtained alongside the syn-dimer from the racemic sample under similar reaction conditions. X-ray structure analysis of the dimers confirmed the mutual biconcave and convex-concave configuration of their TBTQ moieties and the preservation of the orthogonal orientation of the indane wings within each of them.
一种新型的手性三苯并三嗪衍生物，带有邻溴苯胺核，被合成并进行了光学拆分。通过手性辅助的 Buchwald-Hartwig 氨化反应，将单个对映异构体（其绝对构型通过单晶 X 射线结构分析得到确认）立体选择性地转化为相同的吡嗪稠合的 syn-双 TBTQ 衍生物。在相似的反应条件下，从外消旋样品中还获得了相应的非对映异构体 anti-二聚体。从二聚体的 X 射线结构分析证实了它们的 TBTQ 部分的相互双凹和凸凹构型，以及每个部分中茚烷翼的正交取向得以保留。
