32
LIANG AND CANARY
(m, 2H), 7.66 (d, J 5 8.0 Hz, 1H), 7.58 (t, J 5 6.9 Hz, 1H), Hz, 1H), 8.13 (m, 2H), 7.78 (d, J 5 8.1 Hz, 1H), 7.72 (t, J 5
7.39 (m, 2H), 5.81 (m, 1H), 5.23 (d, J 5 17.2 Hz, 1H), 5.13 7.7 Hz, 1H), 7.55 (m, 2H), 7.39 (d, J 5 8.3 Hz, 1H), 7.32
(d, J 5 10.6 Hz, 1H), 4.52 (m, 2H), 4.09 (d, J 5 14.5 Hz, (d, J 5 7.9 Hz, 1H), 7.14 (t, J 5 6.3 Hz, 1H), 4.36 (s, 2H),
1H), 3.94 (d, J 5 14.5 Hz, 1H), 3.48 (m, 1H), 2.58 (m, 3H), 4.16 (m, 2H), 3.85 (m, 1H), 2.70 (m, 2H), 2.36 (m, 1H),
1.80-2.02 (m, 5H); 13C-NMR (CDCl3, 100 MHz): d 174.42, 2.10 (m, 1H), 2.06 (s, 3H); 13C-NMR (CDCl3, 100 MHz):
159.76, 147.65, 136.38, 131.91, 129.40, 129.07, 127.53, d 175.31, 159.92, 158.95, 148.18, 146.39, 137.64, 137.28,
127.31, 126.08, 120.35, 118.66, 65.47, 60.03, 54.04, 32.84, 130.18, 127.73, 127.62, 127.37, 126.72, 123.11, 122.45,
30.57, 15.37; MS (ESI-MS) calcd. for C18H22N2O2S (m/z), 120.46, 63.97, 56.92, 56.05, 31.31, 28.38, 15.24; 1H-NMR
330.1; found, 331.2 (M 1 H1).
(DMSO-d6, 400 MHz): d 8.48 (d, J 5 4.8 Hz, 1H), 8.30 (d,
J 5 8.6 Hz, 1H), 7.95 (m, 2H), 7.73 (m, 2H), 7.58 (m, 2H),
7.48 (d, J 5 7.8 Hz, 1H), 7.23 (t, J 5 6.3 Hz, 1H), 4.13 (m,
2H), 3.98 (m, 2H), 3.50 (m, 1H), 2.45-2.64 (m, 2H), 1.98
(m, 2H), 1.92 (s, 3H); 13C-NMR (DMSO-d6, 100 MHz):
d 173.90, 160.43, 159.45, 148.72, 146.82, 136.52, 136.34,
129.41, 128.39, 127.73, 126.92, 126.10, 122.65, 122.10,
120.81, 61.43, 57.30, 56.79, 30.26, 28.68, 14.31; MS (ESI-
MS) calcd. for C21H23N3O2S (m/z), 381.2; found, 382.2 (M
1 H1).
N-quinaldyl-N-picolyl-L-methionine allyl ester (7)
To a solution 2-picolylchloride (1.16 g, 9.1 mmol) in 45
ml of acetone was added anhydrous NaI (2.22 g, 14.8
mmol). The mixture was heated to reflux under nitrogen
for 2 h. The solvent was removed followed by addition of
200 ml of water and 200 ml of methylene chloride. The
organic layer was separated and washed with 200 ml of
sodium thiosulfate solution (5%). The collected organic
phase was dried over anhydrous Na2SO4 and filtered. The
solvent was removed and the residue was used for the
next step without further purification. N-quinaldyl-L-methi-
[ZnII-1]ClO4
To a methanolic solution of Zn(ClO4)2ꢂ6H2O (48.8 mg,
onine allyl ester 5 (1.2 g, 3.6 mmol) and K2CO3 (1.5 g, 0.131 mmol in 5 ml methanol) was added a solution of
10.9 mmol) in 2 ml of dry DMF was stirred at room temp compound 7 (50 mg, 0.131 mmol in 5 ml methanol) (CAU-
for 30 min. The above 2-picolyliodide 5 residue in 3 ml of TION! Perchlorate salts of metal complexes with organic
dry DMF was added to the reaction mixture. The solution ligands are potentially explosive. They should be handled
was stirred for 17 h at 508C before DMF was removed via in small quantities and with caution.). The solution was
vacuum. The residue was extracted with CH2Cl2 and H2O, stirred for 30 min. An off-white precipitate was filtered and
the organic phase was further washed with H2O and satu- dried under vacuum to yield 52.5 mg (74%) of the complex.
rated brine, and then dried over anhydrous Na2SO4. After 1H-NMR (DMSO-d6, 400 MHz): d 8.88 (d, J 5 5.2 Hz, 1H),
removal of most of the solvent, the residue was subjected 8.76 (m, 2H), 8.68 (d, J 5 8.5 Hz, 1H), 8.58 (d, J 5 4.6 Hz,
to column chromatography (alumina, hexane/ethyl acetate 1H), 8.54 (d, J 5 8.5 Hz, 1H), 8.16 (m, 2H), 8.04 (d, J 5 7.7
1
8:1) to yield 0.54 g (35%) of the compound as an oil. H- Hz, 1H), 7.98 (m, 2H), 7.87 (t, J 5 7.7 Hz, 1H), 7.68-7.79
NMR (CDCl3, 400 MHz): d 8.52 (d, J 5 4.8 Hz, 1H), 8.09 (m, 4H), 7.62 (d, J 5 8.0 Hz, 1H), 7.54 (d, J 5 8.5 Hz, 1H),
(d, J 5 8.5 Hz, 1H), 8.05 (d, J 5 8.4 Hz, 1H), 7.78 (d, J 5 7.40 (d, J 5 7.7 Hz, 1H), 7.34 (t, J 5 6.4 Hz, 1H), 4.52-4.60
8.2 Hz, 1H), 7.69 (t, J 5 6.9 Hz, 1H), 7.60 (m, 2H), 7.51 (t, (m, 2H), 4.29-4.49 (m, 3H), 4.08-4.23 (m, 2H), 3.97 (d, J 5
J 5 6.9 Hz, 1H), 7.44 (d, J 5 7.8 Hz, 1H), 7.11 (t, J 5 6.3 17.2 Hz, 1H), 3.49 (m, 1H), 3.14 (m, 1H), 2.90-3.01 (m,
Hz, 1H), 5.98 (m, 1H), 5.39 (d, J 5 17.2 Hz, 1H), 5.29 (d, J 2H), 2.59-2.78 (m, 2H), 2.26-2.39 (m, 2H), 2.15 (s, 3H),
5 10.4 Hz, 1H), 4.68 (d, J 5 5.8 Hz, 2H), 4.21 (m, 2H), 2.13 (s, 3H), 1.98-2.10 (m, 2H); 13C-NMR (DMSO-d6, 100
4.07 (s, 2H), 3.70 (m, 1H), 2.66 (m, 1H), 2.56 (m, 1H), 2.12 MHz): d 173.43, 173.38, 159.58, 157.56, 155.68, 154.67,
(m, 2H), 2.01 (s, 3H); 13C-NMR (CDCl3, 100 MHz): 148.06, 147.17, 144.61, 144.23, 141.62, 141.43, 140.34,
d 172.39, 160.28, 159.55, 149.16, 147.62, 136.36, 136.32, 140.04, 131.97, 131.56, 128.77, 128.51, 128.39, 127.80,
132.10, 129.38, 129.07, 127.50, 127.32, 126.16, 123.07, 127.50, 126.11, 125.73, 125.12, 124.87, 124.12, 123.83,
122.01, 120.90, 118.73, 65.34, 62.09, 58.10, 57.59, 30.97, 122.16, 121.50, 67.83, 64.13, 59.77, 55.30, 55.23, 54.66,
29.24, 15.22; MS (ESI-MS) calcd. for C24H27N3O2S (m/z), 32.31, 26.21, 25.74, 14.56, 14.46; Elemental Anal. Calcd. for
421.2; found, 422.1 (M 1 H1).
C21H22ClN3O6SZnꢂ0.5H2O: C, 45.50; H, 4.18; N, 7.58;
Found: C, 45.80; H, 3.77; N, 7.47; MS (ESI-MS) calcd. for
C21H22N3O2SZn (m/z), 444.1; found, 444.1.
N-quinaldyl-N-picolyl-L-methionine (1)
A solution of N-quinaldyl-N-picolyl-L-methionine allyl
ester 7 (0.42 g, 1 mmol) in dry THF (11 ml) was treated
with morpholine (1 ml, 10 mmol) and Pd(PPh3)4 (114 mg,
[CuI-1]PF6
Coumpound
7
(10 mg, 0.026 mmol) and
0.1 mmol), and stirred for 12 h at room temp before re- CuI(CH3CN)PF6 (20 mg, 0.053 mmol) were mixed in 2 ml
moval of the solvent under vacuum. The residue was dis- of CD3CN in a glove box and the solution was allowed to
solved in 200 ml of CH2Cl2 and washed with 0.1 M HCl. stand for 30 min. The filtrate was used for NMR measure-
1
The aqueous layer was neutralized with saturated ments. H-NMR (CD3CN, 400 MHz): d 8.65 (b, 1H), 8.38
NaHCO3 until pH 5 6–7, and then extracted with CH2Cl2. (m, 2H), 7.93 (d, J 5 8.0 Hz, 1H), 7.81 (m, 2H), 7.61 (t, J 5
The organic phase was dried over Na2SO4. After removal 7.5 Hz, 1H), 7.45 (d, J 5 8.5 Hz, 1H), 7.38 (m, 2H), 4.48
of most of the solvent, the residue was chromatographed (m, 2H), 4.26 (m, 2H), 3.61 (m, 1H), 2.80 (m, 1H), 2.54
(silica gel, DCM/MeOH 50:1) to yield 0.3 g (79%) of the (m, 1H), 2.15 (m, 2H), 2.05 (s, 3H); MS (ESI-MS) calcd.
1
product. H-NMR (CDCl3, 400 MHz): d 8.49 (d, J 5 4.2 for C21H23N3O2SCu (m/z), 444.1; found, 444.1.
Chirality DOI 10.1002/chir