An Easy and Multigram‐Scale Synthesis of Versatile AA‐ and AB‐Type m‐Terphenylenes as Building Blocks for Kinked Polyphenylenes

Abstract

A set of m‐terphenylenes having a readily functionalizable hydroxy group as well as either symmetric AA‐type or unsymmetric AB‐type halide termini have been prepared on a several‐gram scale. The synthesis was carried out on the basis of the Suzuki–Miyaura cross‐coupling in combination with a TMS masking strategy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Synthesis, Structure and Conformation of Terphenylene‐Derived Oxacalixaromatics

“…and the Supporting Information). [12] The cyclooligomerization of 1 with 1,5-difluoro-2,4-dinitrobenzene (2) in the presence of Cs 2 CO 3 in DMSO at 50°C for 3 h resulted in the formation of the expected terphenylene-based oxacalix[4]arene 9 in a yield of 81.8 %. No larger terphenylene-based oxacalix[n]arenes (n Ͼ 4) were detected.…”

Rational Monomer Design towards 2D Polymers: Synthesis of a Macrocycle with Three 1,8‐Anthrylene Units

“…Compounds 2-4 were selected as building blocks for 1 (Scheme 4). Starting from the previously reported compound 5, [19] the m-terphenylene bridge 2 was prepared by Suzuki-Miyaura cross-coupling (SMC), in which the reactivity difference between bromo and iodo aromatics [20] was combined with a trimethylsilyl (TMS) masking strategy (Scheme 4 a). [21] Compound 5 was first subjected to SMC with 6 [20c] to give 7, followed by electrophilic replacement of the TMS group of 7 by iodide with iodine monochloride (ICl).…”

Synthesis of Shape‐Persistent Macrocycles with Three 1,8‐Diazaanthracene Units and Their Packing in the Single Crystal

“…Synthesis of macrocycles 3 a – c is delineated in Schemes and . The bridging building blocks 12 and 13 were synthesized from the known 3‐bromo‐5‐iodo‐toluene ( 8 ) 17. The different reactivity of its two halogens was used for the selective Sonogashira coupling with TIPSA.…”

“…The remaining bromide was further reacted with bis(pinacolato)diboron under palladium catalysis to give 10 . Double Suzuki coupling of 9 with 3,5‐dibromobenzyl alcohol17 afforded 11 . This reaction was particularly easy to perform and gave compound 11 in quantities of up to 50 g. Complete desilylation of 11 with tetrabutylammonium fluoride (TBAF) resulted in 12 , while the mono‐desilylation of 11 with TBAF in a 1.15:1 stoichiometry afforded 13 after purification.…”