Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease

Way-Zen Lee, Huan Sheng Tseng, Tzu Li Wang, Hui Lien Tsai, Ting Shen Kuo

研究成果: 雜誌貢獻文章

11 引文 (Scopus)

摘要

A disubstituted benzoate polydentate ligand, 2,6-bis[bis(pyridinyl-2- methyl)aminoethoxyl]benzoate (HL), was prepared to synthesize nickel mimics for the active site of urease. Reaction of the deprotonated L- with Ni(ClO4)2 · 6H2O afforded a dinickel complex, [LNi2(CH3CN)(THF)](ClO4)3 (1), characterized by UV/vis spectroscopy and X-ray crystallography. Addition of urea to an acetonitrile solution of 1 afforded a dinickel urea adduct, [LNi2(urea)2](ClO4)3 · 2CH3CN (2), which was structurally and spectroscopically characterized. 1H NMR and ESI-MS spectra of 2 both evidenced that urea molecules remained coordinated to the nickel centers of 2 in solution. With the inspiration of urea coordination to the nickel centers of 1, the conjugate additions of thiophenols to α,β-enones catalyzed by complex 1 were examined and found to proceed in good yields. In contrast, the same catalytic reaction by Ni(ClO4)2 · 6H2O and HL was far less effective. Also, addition of NaOAc or NaOAcPh2 to an acetonitrile solution of 1 gave tetranuclear nickel complexes, [LNi 2-(μ-OAc)]2(ClO4)4 · 3H2O (3) and [LNi2(μ-OAcPh2)] 2(ClO4)4 · 5CH3CN · 2THF (4), and their molecular structures determined by X-ray diffraction can be described as dimers of dimers. Each dinickel core of 3 and 4 closely mimics the active site of urease. The magnetic data of 1, 3, and 4 exhibited a very weak antiferromagnetic coupling (J =-0.72 cm-1 for 1,-0.65 cm-1 for 3 and 4) between two metal centers in the dinickel core.

原文英語
頁(從 - 到)2874-2881
頁數8
期刊Organometallics
29
發行號13
DOIs
出版狀態已發佈 - 2010 七月 12

指紋

Urease
Benzoates
Nickel
ureas
Urea
nickel
acetonitrile
Dimers
dimers
inspiration
X ray crystallography
adducts
crystallography
Ultraviolet spectroscopy
x rays
molecular structure
Molecular structure
perchlorate
thiophenol
Metals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

引用此文

Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease. / Lee, Way-Zen; Tseng, Huan Sheng; Wang, Tzu Li; Tsai, Hui Lien; Kuo, Ting Shen.

於: Organometallics, 卷 29, 編號 13, 12.07.2010, p. 2874-2881.

研究成果: 雜誌貢獻文章

Lee, Way-Zen ; Tseng, Huan Sheng ; Wang, Tzu Li ; Tsai, Hui Lien ; Kuo, Ting Shen. / Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease. 於: Organometallics. 2010 ; 卷 29, 編號 13. 頁 2874-2881.
@article{5192dfd6a0a04055bb46b82025e5dbb8,
title = "Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease",
abstract = "A disubstituted benzoate polydentate ligand, 2,6-bis[bis(pyridinyl-2- methyl)aminoethoxyl]benzoate (HL), was prepared to synthesize nickel mimics for the active site of urease. Reaction of the deprotonated L- with Ni(ClO4)2 · 6H2O afforded a dinickel complex, [LNi2(CH3CN)(THF)](ClO4)3 (1), characterized by UV/vis spectroscopy and X-ray crystallography. Addition of urea to an acetonitrile solution of 1 afforded a dinickel urea adduct, [LNi2(urea)2](ClO4)3 · 2CH3CN (2), which was structurally and spectroscopically characterized. 1H NMR and ESI-MS spectra of 2 both evidenced that urea molecules remained coordinated to the nickel centers of 2 in solution. With the inspiration of urea coordination to the nickel centers of 1, the conjugate additions of thiophenols to α,β-enones catalyzed by complex 1 were examined and found to proceed in good yields. In contrast, the same catalytic reaction by Ni(ClO4)2 · 6H2O and HL was far less effective. Also, addition of NaOAc or NaOAcPh2 to an acetonitrile solution of 1 gave tetranuclear nickel complexes, [LNi 2-(μ-OAc)]2(ClO4)4 · 3H2O (3) and [LNi2(μ-OAcPh2)] 2(ClO4)4 · 5CH3CN · 2THF (4), and their molecular structures determined by X-ray diffraction can be described as dimers of dimers. Each dinickel core of 3 and 4 closely mimics the active site of urease. The magnetic data of 1, 3, and 4 exhibited a very weak antiferromagnetic coupling (J =-0.72 cm-1 for 1,-0.65 cm-1 for 3 and 4) between two metal centers in the dinickel core.",
author = "Way-Zen Lee and Tseng, {Huan Sheng} and Wang, {Tzu Li} and Tsai, {Hui Lien} and Kuo, {Ting Shen}",
year = "2010",
month = "7",
day = "12",
doi = "10.1021/om100103u",
language = "English",
volume = "29",
pages = "2874--2881",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Bioinspired catalytic conjugate additions of thiophenols to α,β-enones by a disubstituted benzoate-bridged nickel mimic for the active site of urease

AU - Lee, Way-Zen

AU - Tseng, Huan Sheng

AU - Wang, Tzu Li

AU - Tsai, Hui Lien

AU - Kuo, Ting Shen

PY - 2010/7/12

Y1 - 2010/7/12

N2 - A disubstituted benzoate polydentate ligand, 2,6-bis[bis(pyridinyl-2- methyl)aminoethoxyl]benzoate (HL), was prepared to synthesize nickel mimics for the active site of urease. Reaction of the deprotonated L- with Ni(ClO4)2 · 6H2O afforded a dinickel complex, [LNi2(CH3CN)(THF)](ClO4)3 (1), characterized by UV/vis spectroscopy and X-ray crystallography. Addition of urea to an acetonitrile solution of 1 afforded a dinickel urea adduct, [LNi2(urea)2](ClO4)3 · 2CH3CN (2), which was structurally and spectroscopically characterized. 1H NMR and ESI-MS spectra of 2 both evidenced that urea molecules remained coordinated to the nickel centers of 2 in solution. With the inspiration of urea coordination to the nickel centers of 1, the conjugate additions of thiophenols to α,β-enones catalyzed by complex 1 were examined and found to proceed in good yields. In contrast, the same catalytic reaction by Ni(ClO4)2 · 6H2O and HL was far less effective. Also, addition of NaOAc or NaOAcPh2 to an acetonitrile solution of 1 gave tetranuclear nickel complexes, [LNi 2-(μ-OAc)]2(ClO4)4 · 3H2O (3) and [LNi2(μ-OAcPh2)] 2(ClO4)4 · 5CH3CN · 2THF (4), and their molecular structures determined by X-ray diffraction can be described as dimers of dimers. Each dinickel core of 3 and 4 closely mimics the active site of urease. The magnetic data of 1, 3, and 4 exhibited a very weak antiferromagnetic coupling (J =-0.72 cm-1 for 1,-0.65 cm-1 for 3 and 4) between two metal centers in the dinickel core.

AB - A disubstituted benzoate polydentate ligand, 2,6-bis[bis(pyridinyl-2- methyl)aminoethoxyl]benzoate (HL), was prepared to synthesize nickel mimics for the active site of urease. Reaction of the deprotonated L- with Ni(ClO4)2 · 6H2O afforded a dinickel complex, [LNi2(CH3CN)(THF)](ClO4)3 (1), characterized by UV/vis spectroscopy and X-ray crystallography. Addition of urea to an acetonitrile solution of 1 afforded a dinickel urea adduct, [LNi2(urea)2](ClO4)3 · 2CH3CN (2), which was structurally and spectroscopically characterized. 1H NMR and ESI-MS spectra of 2 both evidenced that urea molecules remained coordinated to the nickel centers of 2 in solution. With the inspiration of urea coordination to the nickel centers of 1, the conjugate additions of thiophenols to α,β-enones catalyzed by complex 1 were examined and found to proceed in good yields. In contrast, the same catalytic reaction by Ni(ClO4)2 · 6H2O and HL was far less effective. Also, addition of NaOAc or NaOAcPh2 to an acetonitrile solution of 1 gave tetranuclear nickel complexes, [LNi 2-(μ-OAc)]2(ClO4)4 · 3H2O (3) and [LNi2(μ-OAcPh2)] 2(ClO4)4 · 5CH3CN · 2THF (4), and their molecular structures determined by X-ray diffraction can be described as dimers of dimers. Each dinickel core of 3 and 4 closely mimics the active site of urease. The magnetic data of 1, 3, and 4 exhibited a very weak antiferromagnetic coupling (J =-0.72 cm-1 for 1,-0.65 cm-1 for 3 and 4) between two metal centers in the dinickel core.

UR - http://www.scopus.com/inward/record.url?scp=77955824840&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77955824840&partnerID=8YFLogxK

U2 - 10.1021/om100103u

DO - 10.1021/om100103u

M3 - Article

AN - SCOPUS:77955824840

VL - 29

SP - 2874

EP - 2881

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 13

ER -