A Triphenylene-Based Triptycene with Large Free Volume Synthesized by Zirconium-Mediated Biphenylation

Abstract

Biphenylation using (Li(THF)(4))(2) x Zr(biphe)(3) of hexabromotriptycenes bearing H (1-H) or Bu (1-Bu) at the bridgeheads gave triptycenes with triphenylene blades. The blades extend both perpendicular and parallel to the 3-fold axis and generate a large intramolecular free volume (IMFV) (1-H, AM1, 710 A(3); cf. triptycene, AM1 71 A(3)). Crystals of 1-H could not be obtained. Triptycene 1-Bu, in which the Bu groups fill the voids near the bridgehead, was crystalline. X-ray diffraction analysis revealed crystal packing with alternating, interlocked corrugated and distorted hexagonal layers.

9‐Stannafluorenes: 1,4‐Dimetal Equivalents for Aromatic Annulation by Double Cross‐Coupling

“…Considering that 1,4‐M 2 can be readily prepared from the corresponding 1,4‐X 2 and, in particular, the structural variation of available 1,2‐X 2 is much broader than that of 1,2‐M 2 : thus mode B‐type annulation could greatly expand the repertoire of accessible PAHs. However, the precedents of mode B‐type annulation were limited to only the reactions of 2,2′‐diborylbiphenyls,4a zirconacyclopentadienes,4b–d [Zr(2,2′‐biphenyldilyl) 3 ][Li⋅(THF) 4 ] 2 ,4e–g 2,2′‐distannylbinaphthyl,4h and 1,4‐dilithiobutadienes4j with 1,2‐dihalobenzenes, and there is still much room for improvement in the scope of the substrates and reagents, yields, and reaction conditions.…”

Recent Developments in Synthesis and Applications of Triptycene and Pentiptycene Derivatives

“…King et al, [38] for example, reported the two new triptycene derivatives 33a and 33b ( Figure 9). King et al, [38] for example, reported the two new triptycene derivatives 33a and 33b ( Figure 9).…”

Synthesis of Triphenylene-Based Triptycenes via Suzuki–Miyaura Cross-Coupling and Subsequent Scholl Reaction

“…1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 54H, -C(CH 3 ) 3 ) ppm; 13 bridgehead-H), 3.84 (s, 18H, Ar-OCH 3 -4'), 3.57 (s, 18H, Ar-OCH 3 -3') ppm; 13 18-7.16 (m, 18H, 3',4',5'-H) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 1456 ( 4',9,…”