Nickel(II) Thiocyanate Complex as a Catalyst for Cross-Coupling Reactions

Seiha Yamaoka; Hiroyuki Fukuoka; Naoki Noda; Kentaro Okano; Masaki Horie; Atsunori Mori

doi:10.1055/a-2060-3179

Synlett, Table of Contents

Synlett 2023; 34(20): 2401-2404
DOI: 10.1055/a-2060-3179

cluster

Special Issue Dedicated to Prof. Hisashi Yamamoto

Nickel(II) Thiocyanate Complex as a Catalyst for Cross-Coupling Reactions

Seiha Yamaoka

^aDepartment of Chemical Science and Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan

,

Hiroyuki Fukuoka

^aDepartment of Chemical Science and Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan

,

Naoki Noda

^aDepartment of Chemical Science and Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan

,

Kentaro Okano

^aDepartment of Chemical Science and Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan

,

Masaki Horie

^bDepartment of Chemical Engineering, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan

,

Atsunori Mori ∗

^cResearch Center for Membrane and Film Technology, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan

^aDepartment of Chemical Science and Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan

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Abstract

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Abstract

A nickel thiocyanate complex was prepared by the reaction of Ni(NCS)₂ with (2S,3S)-2,3-bis(diphenylphosphino)butane (Chiraphos) by following a method reported in the literature. The resulting nickel complex was found to be active in the polymerization reactions of 1,4-dihalobenzenes and 2-halo-3-hexylthiophenes, leading to poly-1,4-phenylenes and poly(3-hexylthiophene-2,5-diyl), respectively. The polymerization in the presence of similar catalysts containing other ligands, such as 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or N-heterocyclic carbenes, also proceeded in a similar manner. Ni(NCS)₂ complexes also successfully catalyzed Suzuki–Miyaura couplings and Buchwald–Hartwig aminations to afford the corresponding biaryls and arylamines, respectively.

Key words

nickel catalysis - nickel thiocyanate complexes - polymerization catalysts - phosphine ligands - Suzuki–Miyaura cross-coupling - Buchwald–Hartwig amination

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References

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31 Poly(3-hexylthiophen-2,5-diyl) (6); Typical Procedure A 20 mL Schlenk tube equipped with a magnetic stirrer bar was charged sequentially with 2-chloro-3-hexylthiophene (5a) (60.8 mg, 0.3 mmol), a 1.0 M solution of TMPMgCl·LiCl in 20 wt % toluene–THF (0.36 mL, 0.36 mmol), and THF (0.3 mL), and the resulting mixture was stirred at rt for 10 min. The mixture was then diluted with THF (3.0 mL) and Ni(NCS)₂[(S,S)-Chiraphos] (2; 1.9 mg, 0.003 mmol) was added. The resulting mixture was stirred at rt for 12 h, then poured into a mixture of hydrochloric acid (0.30 mL) and MeOH (1.0 mL). The precipitate that formed was collected by filtration and the crude product was washed repeatedly with MeOH and hexanes, then dried under reduced pressure; yield: 55.0 mg (67%). The spectroscopic characteristics of 6 were identical to those of an authentic sample. The number-average molecular weight (M _n = 15,700) and the molecular-weight distribution (M _w/M _n =1.7) were determined by SEC analysis with chloroform as an eluent.

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