Multiply bridgehead- and periphery-substituted tribenzotriquinacenes—highly versatile rigid molecular building blocks with C3v or C3 symmetry

Tribenzotriquinacenes that Bear Three Peripheral Pentaphenylphenyl Residues: Steric Crowding at a Bowl‐Shaped Core

“…[8,17] In analogy to the latter compound, [4c] hydrocarbon 5 was subjected to threefold Rieche formylation by use of dichloromethyl methyl ether under titanium-(IV) catalysis (Scheme 2). mer 6b was obtained in 73 % isolated yield after chromatography.…”

“…[16] One of the fascinating features of the conformationally rigid, C 3v -symmetrical TBTQ framework [17,18] is the suitability of the three three-dimensional bays for bridging by C 2 -units, such as 1,2-vinylidene and 1,2-phenylene groups (e.g. A), as first suggested in 2006.…”

Multiple Vinylation of Tribenzotriquinacenes and Fenestrindanes at Their Aromatic Peripheries by Use of Nájera’s Catalyst

“…[2][3][4] A priori, the presence of three aromatic nuclei in tribenzotriquinacenes makes the rich methodology of arene chemistry applicable to these compounds, thus strongly increasing the potential for functionalization and substitution at the molecular periphery. The two different molecular surfaces of the tribenzotriquinacenes have revealed distinct reactivity towards complexation with tricarbonylmetal entities, [5,6] reflecting their recently calculated pronounced electrostatic potential of the concave surface.…”

“…[24] Some examples involving multiple bromination and iodination of congeners of 1 and 2, including compounds 3 and 4 (Scheme 1) and subsequent palladium-catalyzed phenylation and ethynylation reactions have been demonstrated recently. [3,9] While the "exhaustive" Sonogashira and Suzuki coupling of tribenzotriquinacenes 3a and 3b, respectively, was found to occur in very good yields, [3] the corresponding reactions of the fenestrindanes 4a and 4b gave only moderate yields (29-35 %), and a marked propensity for partial reduction of the halogene functionalities. [9,14,[25][26][27] In fact, separation of minor amounts of the corresponding sevenfold C-C coupled fenestrindanes formed as a by-produces in both the Sonogashira and Suzuki coupling reactions proved to be difficult with fenestrindanes.…”

“…int., %) = 1240. 6 3 ), 58.8 (q, 4b-C etc. ), 88.9 (q, 16d-C), 120.7 (t, 1-C, 5-C, 9-C, 13-C), 121.6 (t, β-C), 121.8 (t, βЈ-C), 123.1 (t, 4-C, 8-C, 12-C, 16-C), 134.4 (q, 2-C, 6-C, 10-C, 14-C), 134.9 (q, 3-C, 7-C, 11-C, 15-C), 141.2 (t, α-C), 141.3 (t, αЈ-C …”