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. 2025 Jun 20;27(24):6298-6303.
doi: 10.1021/acs.orglett.5c01388. Epub 2025 Jun 7.

Modular Assembly of Oligo(phenylenevinylene)s via Iterative Linear-Selective Oxidative Heck Reactions with Protected Boronic Acids

Takaki Nojiri  1 , Takashi Nishikata  1
Affiliations

Modular Assembly of Oligo(phenylenevinylene)s via Iterative Linear-Selective Oxidative Heck Reactions with Protected Boronic Acids

Takaki Nojiri et al. Org Lett. .

Abstract

In this paper, we report the development of an iterative cross-coupling (ICC) process utilizing oxidative Heck reactions with a protected boronic acid derivative, oxazaborolidinone, for the efficient synthesis of oligo(phenylenevinylene)s (OPVs). OPVs possess a structure characterized by alternating benzene rings and alkenes, traditionally synthesized through oligomerization of halogenated styrenes. However, this conventional approach is limited in its ability to incorporate different phenylenevinylene units into a single OPV structure. To address this challenge, we have developed a palladium-catalyzed iterative oxidative Heck reaction process employing newly synthesized oxazaborolidinone-protected boronic acids. When applied to the synthesis of structurally diverse OPVs, our methodology achieved the desired products in excellent yields, demonstrating its high efficiency and practical utility in constructing complex molecular architectures.

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Figures

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1
Oligo­(phenylenevinylene).
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Iterative coupling strategies and problems.
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This work: ICC with nonhalogenated organoborons.
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1. para-Substituted OPV
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2. para- and meta-Substituted OPV
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3. ICC Including Amination and Suzuki–Miyaura Couplings
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