4036
L. Li et al. / Tetrahedron Letters 50 (2009) 4033–4036
L
L
Cu
Cu
R
NBS
R
as oxidant
Cu+
L
L
I
4
Cu+/ DIPEA
R
R
R
R
Cu
2
1
3
I-/NBS
II
L is the N ligand such as DIPEA in this reaction mixture
Scheme 2. Two plausible mechanisms for the CuI/NBS/DIPEA-mediated Glaser coupling reaction.
3
CuX
R
X
5
14. Liu, Q.; Burton, D. J. Tetrahedron Lett. 1997, 38, 4371.
15. Fairlamb, I. J. S.; Bauerlein, P. S.; Marrison, L. R.; Dickinson, J. M. Chem. Commun.
2003, 632.
16. Batsanov, A. S.; Collings, J. C.; Fairlamb, I. J. S.; Holland, J. C.; Zhu, J. J. Org. Chem.
2005, 70, 703.
were discussed, and the further application of the CuI/NBS/DIPEA-
mediated Glaser coupling reaction in the construction of designed
sugars and peptide biomolecules is underway in our laboratory.
17. Li, L.; Zhang, G.; Zhu, A.; Zhang, L. J. Org. Chem. 2008, 73, 3630.
18. General procedure for compound 2a–k: A mixture of 1 (1 mmol), CuI(0.095 g,
0.5 mmol), DIPEA (0.167 mL, 1 mmol), and NBS (0.089 g, 0.5 mmol) in CH3CN
(10 mL) was stirred under air at room temperature for the desired time until
complete consumption of starting material as judged by TLC. After the
conventional workup, the residue was purified by column chromatography
(petroleum ether /ethyl acetate) to give products 2a–c and 2e–k. For 2d, the
yield was determined by GC analysis after workup.Spectral data for all new
compounds: Compound 2f 1H NMR (400 MHz, CDCl3), d 4.14 (t, J = 6.0 Hz, 4H),
2.36 (t, J = 6.8 Hz, 4H), 2.05 (s, 6.0H), 1.85 (m, 4H); 13C NMR (100 MHz, CDCl3) d
171.0, 76.1, 65.1, 62.9, 27.3, 20.9, 16.0; HEMS m/z calculated for C14H18O4Na
273.1103, found 273.1101. Compound 2i 1H NMR (400 Hz, CDCl3), d 5.87–5.77
(m, 4H), 5.30 (d, J = 1.2 Hz, 2H), 5.00 (s, 2H), 4.25–4.41 (m, 4H), 4.07–4.03 (m,
2H), 3.86–3.81 (m, 2H), 3.81–3.55 (m, 2H), 2.35 (t, J = 6.8 Hz, 4H), 2.07 (s, 6H),
2.06 (s, 6H), 1.81 (m, 4H); 13C NMR (100 MHz, CDCl3) d 170.8, 170.3, 129.1,
127.6, 94.5, 67.0, 65.7, 65.2, 63.0, 28.3, 21.0, 20.8, 16.1; HEMS m/z calculated
for C30H38O12Na 613.2201, found 613.2201. Compound 2j 1H NMR (400 Hz,
CDCl3), d 6.76 (br s, 2 H), 4.26 (q, J = 7.2 Hz, 4 H), 4.80 (d, J = 5.2 Hz, 4H), 1.30 (t,
J = 7.2 Hz, 6 H); 13C NMR(100 MHz, CDCl3) d 168.6, 150.8, 74.2, 67.9, 62.0, 41.6,
14.1; HEMS m/z calculated for C14H16N2O6Na 331.0906, found 331.0903.
Compound 2k 1H NMR (400 Hz,CDCl3), d 7.72–7.34 (m, 6 H), 7.14–7.09 (m, 4H),
6.67 (d, J = 8 Hz, 2H), 4.90 (m, 2H), 3.77 (s, 6H), 3.21–3.12 (m, 4H) 13C
NMR(100 MHz, CDCl3) d 170.7, 150.2, 135.0, 129.2, 128.7, 127.4, 74.3, 67.8,
53.7, 52.6, 37.5; HEMS m/z calculated for C26H24N2O6Na 483.1532, found
483.1527.
Acknowledgments
This work was supported by the National Natural Sciences
Foundation of China (20672031, 20802017, and 20872029), the
program for Innovative Research Team (in Science and Technology)
in University of Henan Province (2008IRTSTHN002, 2006-HACET-
06), and Innovation Scientists and Technicians Troop Construction
Projects of Henan Province (084100510002).
References and notes
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