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(
NaOH, 80 mg, 3 equiv) was added. The solution was heated and
(C-2, C-3, C-4, or C-5), 96.4 (C-1), 108.2 (C(CH ) ), 108.5 (C(CH ) ),
3
2
3 2
maintained at 608C for 30 min. Completion was indicated by TLC
122.8 (aryl CH), 122.9 (aryl CH), 147.6 (SCH CN ), 166.0 ppm
2 2
with EtOH as an eluent (R =0.15 in EtOH). The mixture was diluted
(CH COOEt); IR: n˜ =3144 (w, cage CÀH), 3041 (w, aryl CÀH), 2986
f
2
with CH Cl (200 mL) and water (150 mL). HCl (20 mL, aqueous,
(m, alkyl CÀH), 2936 (m, alkyl CÀH), 2568 (s, BÀH), 1751 (s, C=O),
1587 (m), 1532 (m), 1455 (m), 1381 (s), 1255 (s, CÀO), 1214 (s, CÀ
2
2
dilute) was added. After phase separation, the organic phase was
À1
dried over MgSO . Solvent removal gave 12 as a red powder,
O), 1173 (m), 1100 (m), 1069 (m), 993 (s), 843 cm (m); MS (ESI+):
4
+
slightly soluble in CH Cl and soluble in MeCN and acetone. Yield:
834.3 [M+Na]
(100%); elemental analysis calcd (%) for
2
2
1
3
3
78 mg (quantitative); m.p. 138–1408C; H NMR (CD CN): d=0.9–
.5 (several brs and m, 16H; BH), 1.13 (t, J(H,H)=7.6 Hz, 3H;
C H B CoN O S : N 3.45, C 37.00, H 6.60; found N 3.60, C 36.83,
25 53 18 2 7 2
H 6.50.
3
3
SCH CH ), 2.39 (m, 2H; SCH CH ), 3.77 (s, 5H; NCH and SCH CN ),
2
3
2
3
3
2
2
8
-[1-(Carboxymethyl)-3-methyl-2-imidazolium
methylthio]-8’-
4
7
.37 (s, 2H; cage CH), 4.41 (s, 2H; cage CH), 4.92 (s, 2H; CH COOH),
2
11
1
(1,2:3,4-di-O-isopropylidene-6-deoxy-a-d-galacto-pyranosylthio)-
3,3’-commo-bis(undecahydro-1,2-dicarba-3-cobalta-closo-unde-
caborate) (1À) (15): Compound 14 (400 mg, 0.49 mmol) was dis-
solved in MeOH (20 mL), and sodium hydroxide (NaOH, 60 mg,
.28 ppm (s, 2H; aryl CH); B{ H} NMR (CD CN): d=À23.8, À17.1,
3
1
3
1
À7.6, À6.1, À5.0, À0.6, 0.6, 9.4 (BS), 13.6 ppm (BS); C{ H} NMR
(
(
CD CN): d=16.7 (SCH CH ), 23.1 (SCH CN ), 27.3 (SCH CH ), 35.5
3 2 3 2 2 2 3
NCH ), 49.0 (CH COOH), 54.0 (cage CH), 55.8 (cage CH), 122.8 (aryl
3
2
3
6
equiv) was added. The solution was heated and maintained at
CH), 122.9 (aryl CH), 146.1 (SCH CN ), 166.0 ppm (CH COOH); IR:
2
2
2
08C for 30 min. Completion was indicated by TLC with EtOH as
n˜ =3145 (w, cage CÀH), 3040 (w, aryl CÀH), 2922 (m, alkyl CÀH),
eluent (R =0.15 in EtOH). The mixture was diluted with CH Cl
2
(200 mL) and water (150 mL). HCl (20 mL, aqueous, diluted) was
added. After phase separation, the organic phase was dried over
2
851 (m, alkyl CÀH), 2566 (s, BÀH), 1737 (s, C=O), 1587 (m), 1530
f
2
À1
(
(
m), 1445 (m), 1262 (m, CÀO), 1102 (m), 989 (m), 841 cm (m); MS
À
+
ESIÀ): 568.2 [MÀH] (100%); MS (ESI+): 570.3 [M+H] (80%); ele-
MgSO . Solvent removal gave 15 as a red powder, soluble in
mental analysis calcd (%) for C H B CoN O S : N 4.92, C 27.43, H
4
1
3
35 18
2
2 2
CH Cl2 and MeCN. Yield: 382 mg (quantitative); m.p. ꢀ1508C
6
.21; found N 5.20, C 27.68, H 6.35.
2
1
(
decomp.); H NMR (CD CN): d=0.9–3.5 (several brs and m, 16H;
3
1
,2:3,4-Di-O-isopropylidene-6-O-trifluoromethanesulfonyl-a-d-
BH), 1.28 (s, 3H; C(CH ) ), 1.31 (s, 3H; C(CH ) ), 1.35 (s, 3H; C(CH ) ),
3 2 3 2 3 2
galactopyranose (13): Compound 13 was synthesized from com-
mercially available 1,2:3,4-di-O-isopropylidene-a-d-galactopyranose
1.46 (s, 3H; C(CH ) ), 2.43 (m, 1H; H-6), 2.59 (m, 1H; H-6’), 3.67 (m,
3 2
1H; H-5), 3.77 (s, 3H; NCH ), 3.79 (s, 2H; SCH CN ), 4.26-4.31 (m,
3
2
3
2
[18]
according to the literature. Yield: 93% (lit. 95%); m.p. 45–468C
2H; H-2, H-4), 4.40 (s, 4H; cage CH), 4.56 (d, J(H,H)=7.6 Hz, 1H;
H-3), 4.93 (s, 2H; CH COOH), 5.38 (d, J(H,H)=4.7 Hz, 1H; H-1), 7.27
(s, 1H; aryl CH), 7.28 ppm (s, 1H; aryl CH); B{ H} NMR (CD CN):
1
3
(
lit. 478C); H NMR (CDCl ): d=1.34 (s, 6H; C(CH ) ), 1.45 (s, 3H;
3
3 2
2
11
1
C(CH ) ), 1.53 (s, 3H; C(CH ) ), 4.15 (m, 1H; H-5), 4.25 (m, 1H; H-4),
3
2
3 2
3
4
.37 (m, 1H; H-2), 4.57-4.67 (m, 3H; H-3, H-6, H-6’), 5.54 ppm (d,
d=À23.8, À17.0, À7.5, À6.1, À5.1, À0.4, 0.5, 9.7 (BS), 13.4 ppm
3
13
1
13
1
J(H,H)=4.8 Hz, 1H; H-1); C{ H} NMR (CDCl , APT): d=24.3
(BS); C{ H} NMR (CD CN, APT): d=23.1 (SCH CN ), 23.8 (C(CH ) ),
3 2 2 3 2
3
(
(
C(CH ) ), 24.8 (C(CH ) ), 25.8 (C(CH ) ), 25.9 (C(CH ) ), 66.1 (C-5), 70.2
C-2, C-3, or C-4), 70.4 (C-2, C-3, or C-4), 70.6 (C-2, C-3, or C-4), 74.7
24.2 (C(CH ) ), 25.3 (C(CH ) ), 25.4 (C(CH ) ), 32.6 (C-6), 35.4 (NCH ),
3 2 3 2 3 2 3
3
2
3 2
3 2
3 2
48.7 (CH COOH), 53.8 (cage CH), 55.7 (cage CH), 68.3 (C-2, C-3, C-4,
2
(
C-6), 96.1 (C-1), 109.1 (C(CH ) ), 110.1 (C(CH ) ), 118.6 ppm (q,
J(C,F)=319.9 Hz, CF3).
or C-5), 70.4 (C-2, C-3, C-4, or C-5), 70.7 (C-2, C-3, C-4, or C-5), 71.2
3
2
3 2
1
(C-2, C-3, C-4, or C-5), 96.4 (C-1), 108.2 (C(CH ) ), 108.5 (C(CH ) ),
3 2
3 2
1
22.8 (aryl CH), 122.9 (aryl CH), 147.5 (SCH CN ), 166.1 ppm
2 2
8
-[1-(Ethoxycarbonylmethyl)-3-methyl-2-imidazolium
methyl-
(
(
1
CH COOH); IR: n˜ =3130 (w, cage CÀH), 3035 (w, aryl CÀH), 2985
2
thio]-8’-(1,2:3,4-di-O-isopropylidene-6-deoxy-a-d-galacto-pyra-
nosylthio)-3,3’-commo-bis(undecahydro-1,2-dicarba-3-cobalta-
closo-undecaborate) (1À) (14): Compound 6 (500 mg, 0.88 mmol)
was dissolved in MeCN (25 mL, anhydrous and degassed). Potassi-
m, alkyl CÀH), 2936 (m, alkyl CÀH), 2567 (s, BÀH), 1743 (s, C=O),
587 (w), 1532 (w), 1384 (s), 1258 (s, CÀO), 1212 (s, CÀO), 1172 (m),
À
1
+
1101 (m), 1068 (s), 990 (m), 840 cm (m); MS (ESI+): 784.3 [M+H]
+
+
(
100%), 806.3 [M+Na] , 822.3 [M+K] ; elemental analysis calcd
um carbonate (K CO , 245 mg, 2 equiv) and 13 (396 mg,
2
3
(%) for C H B CoN O S : N 3.58, C 35.26, H 6.32; found N 3.73, C
3
23
49 18
2
7 2
1
.15 equiv) were added. The mixture was stirred for 12 h and then
5.03, H 6.40.
diluted with CH Cl (200 mL) and water (150 mL). HCl (20 mL, aque-
2
2
ous, diluted) was added slowly (intense bubbling). After phase sep-
Crystal structure of 11: X-ray data were collected with an Oxford
aration, the organic phase was dried over MgSO ; after filtration,
Diffraction CCD Xcalibur-S diffractometer (data reduction with Crys-
4
[23]
[24]
the solvent was removed under reduced pressure. Column chro-
matography was performed with a continuous gradient change of
the eluent (100% CH Cl to CH Cl /MeCN 96:4, v/v) to afford one
Alis Pro, including the program SCALE3 ABSPACK for empirical
absorption correction) and use of MoKa radiation (l=71.073 pm)
and w-scan rotation. The structure was solved by direct meth-
2
2
2
2
[25]
broad orange band (R =0.10, CH Cl /MeCN 96:4, v/v). Solvent re-
ods, and the refinement of all non-hydrogen atoms was per-
f
2
2
[26]
moval gave 14 as a dark red powder, soluble in CH Cl and MeCN.
formed with SHELXL97. Non-hydrogen atoms were refined aniso-
tropically. Positions of hydrogen atoms were calculated by free re-
finement and constrained methods by using the riding model. The
2
2
1
Yield: 606 mg (85%); m.p. 145–1478C; H NMR (CD CN): d=0.9–3.5
3
(
several brs and m, 16H; BH), 1.28 (m, 6H; (CH )C(CH ), OCH CH ),
3 3 2 3
[
27]
1
.30 (s, 3H; C(CH ) ), 1.34 (s, 3H; C(CH ) ), 1.46 (s, 3H; C(CH ) ), 2.40
structure figure (Figure 1) was drawn with the program ORTEP.
Crystallographic data: C H B CoN O S , M=597.13, monoclinic
3
2
3 2
3 2
(
m, 1H; H-6), 2.59 (m, 1H; H-6’), 3.67 (m, 1H; H-5), 3.77 (s, 3H;
15
39 18
2
2 2
NCH ), 3.79 (s, 2H; SCH CN ), 4.20-4.30 (m, 4H; H-2, H-4, OCH CH ),
space
group
P2 /n,
a=1039.73(2),
b=2612.19(7),
c=
3
2
2
2
3
1
3
3
4
.40 (s, 4H; cage CH), 4.56 (d, J(H,H)=7.6 Hz, 1H; H-3), 4.93 (s, 2H;
1059.37(2) pm, b=91.851(2)8, V=2.8757(1) nm , T=À143.0(2)8C,
Z=4, 25056 reflections measured, 5863 reflections used in all cal-
culations, R [I>2s(I)]=0.0327, wR (all data)=0.0712.
3
CH COOEt), 5.38 (d, J(H,H)=4.8 Hz, 1H; H-1), 7.28 ppm (s, 2H; aryl
CH); B{ H} NMR (CD CN): d=À23.8, À17.0, À7.5, À6.1, À5.1, À0.5,
2
11
1
3
1
2
1
3
1
0
.5, 9.8 (BS), 13.5 ppm (BS); C{ H} NMR (CD CN, APT): d=13.4
3
(
(
5
OCH CH ), 23.1 (SCH CN ), 23.8 (C(CH ) ), 24.2 (C(CH ) ), 25.3
2 3 2 2 3 2 3 2
C(CH ) ), 25.4 (C(CH ) ), 32.6 (C-6), 35.4 (NCH ), 49.0 (CH COOEt),
3 2 3 2 3 2
3.8 (cage CH), 55.7 (cage CH), 62.6 (OCH CH ), 68.3 (C-2, C-3, C-4,
2 3
or C-5), 70.4 (C-2, C-3, C-4, or C-5), 70.8 (C-2, C-3, C-4, or C-5), 71.2
ChemBioChem 2016, 17, 308 – 317
315
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