C. Braunshier et al. / Tetrahedron Letters 49 (2008) 7103–7105
7105
2.
Reviews: (a) Dal Cin, M.; Davalli, S.; Marchioro, C.; Passarini, M.; Perini, O.;
Provera, S.; Zaramella, A. Farmaco 2002, 57, 497–510; (b) Vaino, A. R.; Janda, K.
D. J. Comb. Chem. 2000, 2, 579–596; (c) Yan, B. Acc. Chem. Res. 1998, 31, 621–
6
30.
Ishizone, T.; Han, S.; Okuyama, S.; Nakahama, S. Macromolecules 2003, 36, 42–
9.
Keegstra, E.; Zwikker, J.; Roest, M.; Jenneskens, L. J. Org. Chem. 1992, 57, 6678–
680.
Characterization data for compound 2d: H NMR (CDCl
3.
4.
5.
4
6
1
3
): d 3.75–3.44 (m, 32H),
.76 (br s, 1H), 0.83 (s, 9H), 0.00 (s, 6H). 13C NMR (CDCl
): d 72.6 (t), 72.5 (t),
0.7 (t), 70.5 (t, 10C), 70.3 (t), 62.6 (t), 61.7 (t), 25.9 (q, 3C), 18.3 (s), ꢁ5.3 (q, 2C).
Si: C, 54.52, H, 9.98. Found: C, 54.48, H,
2
7
3
Anal. Calcd for
.72.
22 48 9
C H O
9
6.
Experimental procedure for Mitsunobu reaction on solid phase: Diethyl
azodicarboxylate (5 equiv) was added dropwise to a mixture of 1.0 equiv of
polymer-bounded phenol (100–200 mesh, 1% divinylbenzene, Aldrich,
1
.7 mmol/g) in dry DCM/THF = 1/1 (50 mL/g resin) under argon. Then, the
Figure 3. TOF-SIMS images of immobilized sensor molecule on TentaGel (left) and
resin 5d (right).11
monoprotected glycol 2 (5 equiv), dissolved in dry THF, was added and finally
triphenylphosphine was added slowly. The reaction mixture was stirred
overnight, filtered, and the solid residue was washed three times with DCM/
THF = 1/1, DCM, isopropanol, DCM and finally with methanol. The resulting
resin 3 was dried to constant weight in vacuo.
The figures display the elemental distribution of 35Cl within the
samples. Thus, the attached molecules on individual beads of the
resin can be depicted directly via their chlorine atoms, and the cor-
responding intensity gives an indication of the amount of loading.
Further investigations to utilize the TOF-SIMS technique to study
SPOS resins will be undertaken.
7. Braunshier, C.; Hametner, C. QSAR Comb. Sci. 2007, 26, 908–918.
8.
General procedure for preparation of resin 5: Resin 4 was suspended in dry DCM/
DMF = 9/1 (15 mL/g resin), and then 4-(dimethylamino)-butyric acid
hydrochloride (5.0 equiv) and 1-hydroxybenzotriazole (5.0 equiv) were added
in a minimum amount of dry DMF. 4-(N,N-dimethylamino)-pyridine (1.0 equiv)
0
in dry DMF and N,N -diisopropylcarbodiimide (5.0 equiv.) were added to the
mixture and were stirred under argon at room temperature for 2 days. The
resulting suspension was filtered and the solid residue was washed three times
with DMF, then with DCM, and finally with methanol. The resin was dried to
constant weight in vacuo.
Supplementary data
9
.
Kita, R.; Svec, F.; Fréchet, M. J. J. Comb. Chem. 2001, 3, 564–571.
Some representative IR spectra and more examples of gel-phase
C NMR spectra of prepared resins, as well as TOF-SIMS images of
10. TOF-SIMS measurements were carried out on a TOF-SIMS 5 instrument (ION-
1
3
þ
TOF GmbH, Münster, Germany), equipped with a Bi
cluster ion source at
n
þ
2
5 keV energy. Images were recorded using Bi
ion clusters for enhanced
3
secondary ion yield, with a primary ion dose density of 1.0E ions/cm2 to
12
13
13
operate under static SIMS conditions.
1
1. The field of view is always 128 ꢂ 128 pixels, independent from the
The color scale depends on ‘mc value’ (maximum counts per pixel), not on the
tc value’ (total counts).
lm scale.
References and notes
‘
1
1
2. Nagy, G.; Walker, A. V. Int. J. Mass Spectrosc. 2006, 262, 144–153.
3. Verdier, S.; Metson, J. B.; Dunlop, H. M. J. Mass Spectrosc. 2007, 42, 11–19.
1
.
Bayer, E.; Hemmasi, B.; Albert, K.; Rapp, W.; Dengler, M. Peptides, Structure and
Function. Hruby, V. J., Rich, D. H., Eds; Proceedings of the 8th American Peptide
Symposium; Pierce Chemical Company: Rockford, IL, 1983; pp 87–90.