1,3,5-Tris(2′-aminophenyl)benzene: A Novel Platform for Molecular Receptors

Abstract

The synthesis of a novel, rigid, aromatic platform for molecular receptors is described. 1,3,5-Tris(2′-aminophenyl)benzene was prepared via Suzuki-Miyaura cross-coupling reactions of 2-aminophenylboronic acid with 1,3,5-triiodobenzene in the ­presence of Ba(OH)₂, Pd(OAc)₂ and (2-biphenyl)dicyclohexyl­phosphine. Alternatively, one-pot borylation of 2-bromoaniline and cross-coupling of the resulting boronate ester with 1,3,5-triiodo­benzene was investigated.

Key words

molecular scaffolds - amines - biaryls - cross-coupling - palladium

References and Notes

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15

Experimental Procedure (Table 1, Entry 4) and Spectroscopic Data for 1.
An oven-dried resealable Schlenk tube containing a magnetic stir bar was charged with 6 (1 mmol), 3 (0.3 mmol), Pd(OAc)₂ (3 mol%), 7 (9 mol%) and Ba(OH)·8H₂O (6 mmol). The Schlenk tube was capped with a rubber septum and then evacuated and backfilled with argon. Dry dioxane was added and the resulting mixture was heated at 85 °C with vigorous stirring for 24 h. The reaction mixture was then allowed to cool to r.t., filtered though a pad of Celite^® and concentrated under reduced pressure. The crude material obtained was purified by flash chromatography on silica (MeOH-CH₂Cl₂, 2:98) to afford 1 as colorless solid. R _f = 0.42 (MeOH-CH₂Cl₂, 3:97); mp 221-223 °C (toluene). ¹H NMR (200 MHz, CDCl₃): δ = 7.58 (s, 3 H), 7.24-7.12 (m, 6 H), 6.87-6.76 (m, 6 H), 3.72 (br s, 6 H). ¹³C NMR (50 MHz, CDCl₃): δ = 143.5, 140.7, 130.5, 128.7, 128.2, 126.9, 118.8, 115.8. HRMS (ESI): m/z calcd for C₂₄H₂₁N₃Na: 374.1633; found: 374.1640 [M + Na]⁺.