R. Gawin et al. / Tetrahedron 66 (2010) 1051–1056
1055
(
2
2
d, 1H, J¼8.12), 6.78 (br s), 4.96 (q, 1H, J¼6.82), 4.22 (s, 4H), 2.68 (t,
H, J¼6.7), 2.48 (br s, 6H), 2.45(s, 6H), 2.44 (br s, 6H), 2.42 (s, 6H),
.07 (s, 3H), 2.02 (s, 3H), 1.96 (s, 3H), 1.82 (m), 1.51 (m), 1.30–1.48
(
1
1
2
3
1
1
(
m), 1.24 (s, 3H), 1.17–1.21 (m), 1.08–1.20 (m, 6H), 0.86–0.82 (m,
13
2H); C NMR (200 Hz, CDCl
9.64, 19.65, 19.87, 20.38, 20.92, 22.08, 23.11, 23.12, 24.66, 24.79,
4.89, 25.53, 29.81, 30.85, 30.87, 32.01 32.75, 32.77, 35.34, 37.33,
7.39, 37.41, 37.45, 37.55, 38.32, 38.86, 79.09, 101–115(m), 116.43,
22.70, 123.16, 123.56, 124.50, 124.67, 125.05, 126.11, 127.00, 129.56,
29.64, 130.64, 134.45, 138.54, 146.60, 150.19, 151.22, 156.16, 159.39
Cl ):
¼2926,
3
):
d
¼11.87, 12.36, 16.58, 19.57, 19.59,
t, J¼30.1), 160.75 (t, J¼29,2), 170.35, 184.19; IR (CH
2
2
n
ꢁ
1
1
788, 1484, 1298, 940 cm
.
4.6. N-(2-hydroxyethyl)-N,N-dimethyl-1-hexadecanaminium
methylsulfate (16b)
To
decanaminium chloride (16a, 700.1 mg, 2.0 mmol) in CH
1 mL) dimethyl sulfate (252.3 mg, 2.0 mmol) was added. Mixture
was stirred for 30 min. and evaporated to give white crystalline
a solution of N-(2-hydroxyethyl)-N,N-dimethyl-1-hexa-
12
2
Cl
2
(
1
solid (845 mg, 99%). H NMR (200 MHz, CDCl
3
):
d
¼4.06 (br s, 2H),
3
(
.70 (m, 2H), 3.60 (m, 2H), 3.39 (s, 6H), 3.23, 1.72 (m, 2H), 1.32–1.24
13
comp, 26H), 0.85 (t, 3H, J¼7.0); C NMR (50 MHz, CDCl
3
):
d¼65.94,
6
2
5.59, 56.25, 54.60, 53.43, 51.62, 31.92, 29.70, 29.67, 29.52, 29.45,
9.37, 29.22, 26.29, 22.79, 22.70, 14.13; HRMS (ESI): calcd for m/z
44NO: 314.3417; found: 314.3409; IR (thin-film):
calcd for C20
H
ꢁ
1
n
¼3437, 2922, 2852, 1640, 1468, 1249, 1225, 1061, 1006, 766 cm
.
4
.7. Compound 17
Figure 3. Different stages of RCM of 20. a): substrate 20 under water; b) greenish
emulsion formed after adding catalyst 17 and stirring; c) product 21 after removing of
water and washing with ethanol; d) product 21 crystallized from ethanol.
In a Schlenk 16b (85 mg, 0.2 mmol) was dissolved in dry CH
2
Cl
2
(3 mL) under argon flow. Next hexafluoroglutaric anhydride (27
mL,
0
.2 mmol) in dry CH Cl (2 mL) was added in portions and mixture
2
2
4
.4. Mono-(2,5,7,8-tetramethyl-2-(4,8,12-trimethyl-tridecyl)-
was stirred for 30 min. Then 9 (124 mg, 0.2 mmol) was added and
mixture was stirred for 5 min. Next n-hexane (5 mL) was added.
chroman-6-yl) 2,2,3,3,4,4-hexafluoroglutarate (13)
CH
solid was filtered and dried (250 mg, 99%). H NMR (400 MHz,
CDCl ):
2 2
Cl was evaporated and precipitated green microcrystalline
1
In a Schlenk tocopherol (12, 861.4 mg, 2.0 mmol) was dissolved
in dry CH
tilled pyridine was added (0.17 mL, 2.0 mmol). Then hexa-
fluoroglutaric anhydride (0.27 mL, 2.0 mmol) in dry CH Cl (5 mL)
2
Cl
2
(10 mL) under argon flow in dark room. Freshly dis-
3
d¼16.63 (s, 1H), 10.56 (s, 1H), 7.54–7.58 (m, 1H), 7.05 (s, 4H),
6.98–7.03 (m, 2H), 6.87 (d, J¼8.12 Hz, 1H), 4.99 (q, J¼6.85 Hz, 1H),
4.21 (s, 2H), 4.18 (s, 4H), 2.44–2.47 (m, 2H), 2.43 (br s, 6H), 2.41 (s,
6H), 2.38 (s, 6H), 2.36 (s, 2H), 2.34 (s, 3H), 2.27 (s, 3H), 1.36 (d,
2
2
was added in portions and mixture was stirred for 30 min. Next
mixture was washed with diluted hydrochloric acid and water.
13
J¼6.84 Hz, 3H), 1.16–1.25 (m, 12H), 0.90 (t, J¼12.4, 5.4 Hz, 3H);
NMR (200 Hz, CDCl ):
¼209.62, 182.77, 154.42, 146.63, 139.34,
130.34, 129.61, 129.50, 126.85, 122.36, 119.16, 112.90, 96.96, 83.93,
77.66, 77.02, 77.39, 54.88, 51.32;IR (CH Cl ):
¼2986, 1756, 1484,
C
Organic layer was dried over MgSO
4
and passed trough pad of silica,
3
d
which was additionally washed with acetone. After evaporation of
1
solvent title product was obtained as orange oil (933 mg, 71%). H
2
2
n
ꢁ
1
NMR (400 MHz, CDCl
H), 2.02 (s, 3H), 1.98 (s, 3H), 1.79 (m), 1.52 (m), 1.32–1.44 (m), 1.27
s, 3H), 1.20–1.25 (m), 1.00–1.23 (m, 6H), 0.83–0.87 (m, 12H);
NMR (100 MHz, CDCl ):
9.66, 19.72, 20.56, 20.99, 22.61, 22.71, 23.80, 24.43, 24.79, 24.81,
3
):
d
¼6.75 (br s), 2.60 (t, 2H, J¼6.7), 2.10 (s,
1298, 941 cm
.
3
(
13
C
Acknowledgements
3
d
¼11.68, 11.80, 12.52, 19.56, 19.59, 19.63,
1
2
3
K.G. thanks Foundation for Polish Science for the Mistrz pro-
fessorship. R.G. thanks for KBN for grant (N N204 155436).
7.97, 29.70, 30.87, 30.93, 32.66, 32.76, 32.78, 37.27, 37.31, 37.38,
7.43, 37.47, 37.50, 39.35, 39.94, 75.46, 105–111(m), 117.93, 123.70,
24.44, 126.05, 139.66, 150.26, 157.49 (t, J¼30.2), 160.73 (t, J¼29.3);
IR (CH Cl ):
¼3550, 2952, 2928, 2869,1790, 854, 836, 781, 727,
73 cm ; HRMS (EI): calcd for C34 : 652.3562; found:
52.3545.
1
References and notes
2
ꢁ
2
n
1
6
6
50 6 5
H F O
1. (a) Handbook of Metathesis; Grubbs, R. H., Ed.; Viley-VCH: Weinheim, 2003; (b)
Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18–29; (c) Connon, S. J.;
Blechert, S. Angew. Chem., Int. Ed. 2003, 42, 1900–1923; (d) Astruc, D. New J.
Chem. 2005, 29, 42–56; (e) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem.,
Int. Ed. 2005, 44, 4490–4527; (f) Boeda, F.; Clavier, H.; Nolan, S. P. Chem. Com-
mun. 2008, 2726–2740.
4
.5. Compound 14
2
3
. Burtscher, D.; Grela, K. Angew. Chem., Int. Ed. 2009, 48, 442–454.
. (a) Binder, J. B.; Raines, R. T. Curr. Opin. Chem. Biol. 2008, 12, 767–773; (b) Lin, Y.
A.; Chalker, J. M.; Floyd, N.; Bernardes, G. J. L.; Davis, B. G. J. Am. Chem. Soc. 2008,
130, 9642–9643.
To a solution of 13 (131 mg, 0.2 mmol) in dry CH
was added (124 mg, 0.2 mmol) and mixture was stirred for 5 min.
Next n-hexane (5 mL) was added in portions. CH Cl was evapo-
rated and precipitated green microcrystalline solid was filtered and
dried (251 mg, 99%). 1H NMR (400 MHz, CDCl
):
¼16.63 (s, 1H),
0.57 (s, 1H), 7.56–7.58 (m, 1H), 7.08 (s, 4H), 7.06–7.02 (m, 2H), 6.82
2 2
Cl (5 mL) 9
2
2
4
5
. Binder, J. B.; Blank, J. J.; Raines, R. T. Org. Lett. 2007, 9, 4885–4888.
. (a) Complex 1: Lynn, D. M.; Mohr, B.; Grubbs, R. H. J. Am. Chem. Soc. 1998, 120,
3
d
1627–1628; (b) Complex 2: Hong, S. H.; Grubbs, R. H. J. Am. Chem. Soc. 2006,
128, 3508–3509; (c) Complex 3: Jordan, J. P.; Grubbs, R. H. Angew. Chem., Int. Ed.
1