Materials and Bioengineering, Kansai University, Suita ...€¦ · Compounds 3a1, 3b1,2, 3c1,2,...

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Electronic Supplementary Information

Surfactant-free single-nano-sized colloidal Cu nanoparticles for use as an

active catalyst of Ullmann-coupling reaction

Yuto Isomura,a Takashi Narushima,b Hideya Kawasaki,a Tetsu Yonezawab and

Yasushi Obora*a

a Department of Chemistry and Materials Engineering, Faculty of Chemistry,

Materials and Bioengineering, Kansai University, Suita, Osaka 564-8680, Japan b Division of Materials Science and Engineering, Faculty of Engineering, Hokkaido

University, Sapporo, Hokkaido 060-8628, Japan.

E-mail: obora@kansai-u.ac.jp

Table of Contents

S2: General

S2-6: Experimental details

S6: References

S7: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3a.

S8: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3b.

S9: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3c.

S10: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3d.

S11: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3e.

S12: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3f.

S13: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3g.

S14: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3h.

S15: Copies of 1H (400 MHz, CDCl3) and 13C NMR spectra for 3i.

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General

GLC analysis was performed with a flame ionization detector using a 0.22 mm×25

m capillary column (BP-5). 1H and 13C NMR were measured at 400 and 100 MHz,

respectively, in CDCl3 with Me4Si as an internal standard. The products were

characterized by 1H NMR, 13C NMR, and GC-MS. The yields of products were

estimated from the peak areas based on the internal standard technique using GC.

All starting materials were commercially available and used without any purification.

CuCl2 was obtained from Wako Chemical Co. All solvents and other regents were

obtained from Wako Chemical Co, TCI and ALDRICH and were used without further

purification.

Compounds 3a1, 3b1,2, 3c1,2, 3d1,2, 3e2, 3f2, 3g2, 3h1, 3i1 were reported previously.

Experimental details

Preparation of Cu NPs. A solution of 15 L of 0.1 M aqueous CuCl2 was added to 15

mL of N, N-dimethylformamide (DMF) that had been preheated to 140 oC, and the

DMF solution was refluxed in a 140 oC oil bath with stirring for 8 h. The surfactant-free

copper nanoparticles (Cu NPs) were obtained as the 0.1 mM Cu NPs in DMF. After

vacuum evaporation of excess solvent, the residue was redissolved in selected solvents

such as methanol, acetonitrile (MeCN), and N-methylpyrrolidone (NMP) for the TEM

measurement and the Ullmann O-Arylation.

Preparation of 0.01 mM Cu NPs in DMF (10-3 mol %)

The DMF solution of 1 mL of the prepared 0.1 mM Cu NPs was added to 10 mL of

DMF, and the solution of 0.01 mM Cu NPs in DMF was prepared.

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Photophysical property. Fluorescence excitation and emission spectra were obtained

on a JASCO FP-6200 fluorospectrophotometer. at UV excitation of 350 nm (Figure S1)

Figure S1. Photoluminescene emission spectra of DMF-protected Cu NPs.

Figure S2. The high-magnification TEM image of Cu NPs showed that the crystal

lattice fringes are 0.2 nm apart, which agrees with the d value of the (111) planes of the

metallic Cu crystal. Bar : 3nm.

0

200

400

600

800

1000

1200

1400

1600

350 400 450 500 550 600

PL

Inte

nsi

ty (

a.u.

)

Wavelength (nm)

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X-ray photoelectron spectroscopy (XPS). X-ray photoelectron spectra were recorded

with a Quantera SXM spectrometer (Physical Electronics, Inc.) using the

monochromatic Al Kα line at 1486.7 eV. The base pressure was approximately 2 × 10-8

Torr. To compensate for charging effect, binding energies were referenced to C 1s at

284.7 eV of hydrocarbon.

9309409509609700

200

400

600

800

1000

1200

1400

1600

1800

Binding Energy (eV)

Inte

nsity

(arb

. uni

ts)

Cu2p932.0 eV

934.4 eV

Figure S3. XPS spectrum of dried Cu NCs

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Transmission electron microscopy (TEM). A drop of Cu NPs dispersed in methanol

was placed on a carbon-coated Cu grid, and HR-TEM (high resolution TEM) image was

obtained with a Hitachi H-9500 at an acceleration voltage of 300 kV. The raw

magnification of the image was 1,000,000.

Dynamic Light Scattering (DLS). A Nanoparticle analyser model SZ-100 with a

100mW laser and an interference optical filter at wavelength of 532nm (HORIBA,

Japan) was used to perform dynamic light scattering for samples 200 L (40 mM

solution in DMF) in volume . The DLS measurement was performed at 25 oC.

A typical reaction procedure for Cu NPs catalyzed Ullmann O-Arylation of 1a with

2a (Table 1, entry 2)

A mixture of iodobenzene 1a (306 mg, 1.5 mmol), 3, 5-dimethylphenol 2a (122 mg,

1.0 mmol), Cs2CO3 (652 mg, 2.0 mmol) and 0.1 mM Cu NPs in DMF (1 mL) as a

catalyst was stirred at 140 oC for 24 h under Ar. The conversions and yields of products

were estimated from peak areas based on an internal standard (tridecane) using GC and

the product 3a was obtained in quantitative yield. The product 3a was isolated by

column chromatography (230-400 mesh silica gel, n-hexane / ethyl acetate = 20 / 1) in

88% yield (174 mg). The highest turnover frequency was achieved 450 for 1 h.

Figure S4. Time course for Ullmann O-Arylation reaction

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A typical procedure for the catalyst-reusing sequence in the Cu NPs-catalyzed

model reaction

After the reaction was performed under the conditions of entry 2, Table 1, iodobenzene

1a (306 mg, 1.5 mmol), 3, 5-dimethylphenol 2a (122 mg, 1.0 mmol) and Cs2CO3 (652

mg, 2.0 mmol) were added to the reaction mixture. It was used next catalytic sequence

under the same reaction conditions as first cycle.

Figure S5. Depiction of the catalyst-reusing

Table S1. Catalyst-reusing

Cycle 1st 2nd 3rd

Yield (%)a >99 51 18 a GC yields (based on 2a) were determined by average of three runs.

References

(1) H. J. Cristau, P. P. Cellier, S. Hamada, J. –F. Spindler and M. Taillefer, Org. Lett., 2004, 6, 913.

(2) A. B. Naidu, E. A. Jaseer and G. Sekar, J. Org. Chem. 2009, 74, 3675.

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3a

PPM

8 6 4 2 0

PPM

200 175 150 125 100 75 50 25 0

O

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3b

PPM

10.0 7.5 5.0 2.5 0.0 -2.5

PPM

200 175 150 125 100 75 50 25 0

O

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3c

PPM

12.5 10.0 7.5 5.0 2.5 0.0 -2.5

PPM

200 175 150 125 100 75 50 25 0

O

OMe

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3d

O

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3e

PPM

10.0 7.5 5.0 2.5 0.0 -2.5

PPM

200 150 100 50 0

O

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S12

3f

PPM

10.0 7.5 5.0 2.5 0.0 -2.5

PPM

200 175 150 125 100 75 50 25 0

O

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3g

PPM

8 6 4 2 0

PPM

200 175 150 125 100 75 50 25 0

O

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3h

PPM

2.5 10.0 7.5 5.0 2.5 0.0 -2.

PPM

200 150 100 50 0

O

MeO

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3i

PPM

2.5 10.0 7.5 5.0 2.5 0.0 -2.5

PPM

200 175 150 125 100 75 50 25 0

O

F3C

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