Synthetic Strategies for the Regioselective Functionalization of Tribenzotriquinacenes

Abstract

The rigid molecular scaffold of the tribenzotriquinacenes (TBTQs) has emerged as a versatile structural platform that possesses unique geometrical features and allows for an orthogonal arrangement of organic functional substituents or convex-concave interactions. In this review, we summarize and discuss important synthetic strategies for a regioselective functionalization at the four distinct positions of the TBTQ basic framework, namely, apical, bridgehead, ortho, and outer rim.1 Introduction2 Structure and Synthesis of TBTQs3 Bridgehead Functionalization4 Outer Rim Functionalization5 ortho-Functionalization6 Apical Functionalization7 Conclusion and Outlook

Controlled Formation of Porous 2D Lattices from C3‐symmetric Ph6−Me‐Tribenzotriquinacene‐OAc3

“…Further purification for STM investigations was performed by reversed phase HPLC (Reprosil C-18-PQ-JASCO semi preparative column, 5 μm, 250 mm × 10 mm) using acetonitrile as eluent. 1 was isolated as a cream-colored crystalline solid (100 mg, 0.108 mmol, 83 %), F p : 248-252 °C, R f : 0.54 (cyclohexane/ ethyl acetate 2 : 1), 1 H NMR (600 MHz, DMSOd 6 ): δ = 7.83 (s, 6H, 1/4-H), 7.24-7.17 (m, 18H, 3'/4'/5'-H), 7.03-7.01(dt, J = 1.910 Hz, 12H, 2'/6'-H), 2.16 (s, 9H, 4b2/8b2/12b2-H), 1.56 (3H, s, CH 3 ) ppm, 13 C NMR (600 MHz, DMSO-d 6 ): δ = 169.66 (C q , À OC(O)Me, C-4b1/8b1/12b1), 141.79 (C q , C-1'), 140.97 (C q , C-8a/4c/4a/12c/12a/8a), 140.55 (C q , C-7/6/3/2/10/11), 128.02 (C t , C-3',4'), 126.82 (C t , C-5'), 125.58 (C t , C-2', 6'), 125.45 (C t , C-1/4/5/8/9/ 12), 95.95 (C q , C-4b/8b/12b), 76.94 (C q , C-12d), 21 The STM measurements were performed under ultra-high vacuum (UHV) conditions (base pressure p � 1 × 10 À 10 mbar). Sample preparation and analysis were performed in two separate chambers.…”

“…Tribenzotriquinacenes (TBTQs) have recently come into focus as model compounds for highly curved, defective graphene structures [16] and are also being investigated as building blocks for highly porous 3D organic frameworks [17,18] . TBTQs can be functionalized in different positions leading to derivatives with functional moieties for sensing, covalent assembly, or molecular recognition [19–22] . The assembly of simple TBTQs has been studied both in crystals [23–25] and on surfaces [26] .…”

“…[17,18] TBTQs can be functionalized in different positions leading to derivatives with functional moieties for sensing, covalent assembly, or molecular recognition. [19][20][21][22] The assembly of simple TBTQs has been studied both in crystals [23][24][25] and on surfaces. [26] On a metal surface, the arrangement of TBTQ and Me-TBTQ was governed by the surface coverage, and showed hexagonal patterns and honeycomb structures.…”

Molecular bowls for inclusion complexation of toxic anticancer drug methotrexate

“…As for the main objectives of this study, we aimed to develop a facile synthetic method 20 for accessing bowl-shaped 1 6+ in addition to its constitutional isomer 2 6+ ( Fig. 2 ).…”