N-Functionalized Azolin-2-ylidene-palladium-Catalyzed Heck Reaction 85
(t, 8H, J = 6 Hz, NCH CH2CH N), 4.88 (s, 4H,
1,3-Difurfuryltetrahydropyrimidinium
Hexafluorophosphate (1b)
2
2
CH C4H3O), 7.07, 7.21, and 7.60 (m, 6H, C4 H O), 8.82
2
3
(s, 1H, 2-CH). 13C NMR (DMSO) δ: 19.1 and 42.7
(NCH2CH2CH2N), 52.9 (CH2C4H3S), 128.1, 128.2,
129.4, and 136.9 (C4H3S), 153.7 (2-CH). Anal. Calcd
for C14H17N2S2PF6: C, 39.81, H, 4.06, N, 6.63. Found:
C, 39.81, H, 4.07, N, 6.63.
This compound was prepared from 1,3-bisfur-
furylaminopropane (2.17 g, 9.27 mmol) CH(OEt)3
(5 mL) and NH4PF6 (1.51 g, 9.27 mmol). Yield:
3.21, 89%, mp 210–211◦C. H NMR (DMSO) δ: 1.94
1
(quin., 4H, J = 5.6 Hz, NCH2CH CH2N), 3.26 (t, 8H,
2
J = 5.6 Hz, NCH CH2CH N), 4.82 (s, 4H, CH C4H3O),
2
2
2
6.22, 6.45, and 7.28 (m, 6H, C4 H O), 10.04 (s,
3
1,3-Di(2-thiophenemethyl)terahydrodi-
azepinium Hexafluorophosphate (2c)
1H, 2-CH). 13C NMR (DMSO) δ: 19 and 42.6
(NCH2CH2CH2N), 50.9 (CH2C4H3O), 110.9, 111.5,
143.9, and 146.9 (C4H3O), 154.7 (2-CH). Anal. Calcd
for C14H17N2O2PF6: C, 43.09, H, 4.39, N, 7.18. Found:
C, 49.09, H, 4.38, N, 7.16.
This compound was prepared from 1,4-bis(2-
thiophenemethyl) aminobutane (1.90 g, 6.77 mmol)
CH(OEt)3 (5 mL) and NH4PF6 (1.10 g, 6.74 mmol).
Yield: 2.24 g, 76%, mp 156–157◦C. 1H NMR (DMSO)
δ: 1.78 (quin., 8H, J = 5.6 Hz, NCH2CH CH CH2N),
2
2
3.66 (t, 8H, J = 5.6 Hz, NCH CH2CH2CH N), 4.86 (s,
1,3-Difurfuryltetrahydrodiazepinium
hexafluorophosphate (1c)
2
2
4H, CH C4H3S), 7.07, 7.25, and 7.60 (m, 6H, C4 H S),
2
3
8.60 (s, 1H, 2-CH). 13C NMR (DMSO) δ: 24.9 and
49.1 (NCH2CH2CH2CH2N), 55.3 (CH2C4H3S), 128.1,
128.3, 129.4, and 137.6 (C4H3S), 158.9 (2-CH). Anal.
Calcd for C15H19N2S2PF6: C, 41.28, H, 4.39, N, 6.42.
Found: C, 41.30, H, 4.38, N, 6.43.
This compound was prepared from 1,4-bisfurfur-
ylaminobutane (0.92 g, 3.70 mmol) CH(OEt)3 (5
mL) and NH4PF6 (0.60 g, 3.68 mmol). Yield: 1.20
g, 81%, mp 107–108◦C. 1H NMR (DMSO) δ: 1.78
(quin., 8H, J = 5.6 Hz, NCH2CH CH CH2N), 3.65 (t,
2
2
8H, J = 5.6 Hz, NCH CH2CH2CH N), 4.68 (s, 4H,
2
2
CH C4H3O), 6.49, 6.59, and 7.73 (m, 6H, C4 H O),
2
3
8.48 (s, 1H, 2-CH). 13C NMR (DMSO) δ: 24.7 and
49.2 (NCH2CH2CH2CH2N), 53.3 (CH2C4H3O), 111.4,
111.6, 144.9, and 148.4 (C4H3O), 159.2 (2-CH). Anal.
Calcd for C15H19N2O2PF6: C, 44.56, H, 4.74, N, 6.93.
Found: C, 44.55, H, 4.74, N, 6.95.
General Procedure for the Heck-Coupling
reaction
Pd(OAc)2 (1.0 mmol%), 1,3-dialkylazolinium salts 1
or 2 (= LHX, 2 mmol%), aryl bromide (1.0 mmol),
styrene (1.5 mmol), t-BuOK (2 mmol), water (3 mL)
and DMF (3 mL) were added to a small Schlenk
tube, and the mixture was heated to 50◦C for 4 h.
At the conclusion of the reaction, the mixture was
cooled, extracted with ethylacetate/hexane (1:5), fil-
tered through a pad of silicagel with copious wash-
ings, concentrated, and purified by flash chromatog-
raphy on silicagel. The purity of the compounds was
checked by NMR and GC, and yields are based on
arylbromide.
1,3-Di(2-thiophenemethyl)imidazolidinium
Hexafluorophosphate (2a)
This compound was prepared from 1,2-bis(2-thio-
phenemethyl)aminoethane (2.3 g, 91.16 mmol)
CH(OEt)3 (5 mL) and NH4PF6 (1.48 g, 9.10 mmol).
Yield: 3.08, 83%, mp 125–126◦C. H NMR (DMSO)
1
δ: 3.79 (s, 8H, NCH CH N), 4.89 (s, 4H, CH C4H3S),
7.01, 7.19 and 7.60 (m, 6H, C4 H S), 8.71 (s, 1H,
2
2
2
3
2-CH). 13C NMR (DMSO) δ: 46 (NCH2CH2N), 48.4
(CH2C4H3S), 128.2, 128.3, 129.6 and 136.2 (C4H3S),
158.0 (2-CH). Anal. Calcd for C13H15N2S2PF6: C,
38.24, H, 3.70, N, 6.86. Found: C, 38.25, H, 3.71,
N, 6.86.
REFERENCES
[1] Herrmann, W. A. Applied Homogeneous Catal-
ysis with Organometallic Compounds; Cornils,
B.; Herrmann, W. A. (Eds.); Wiley-VCH Verlag:
Weinheim, Germany, 2002.
[2] (a) De Meijere, A.; Meyer, F. E. Angew Chem, Int
Ed Engl 1994, 33, 2411; (b) Donnay, A. B.; Overman,
L. E. Chem Rev 2003, 103, 2945–2964.
1,3-Di(2-thiophenemethyl)tetrahydropyrimidi-
nium Hexafluorophosphate (2b)
[3] Farina, V. Adv Synth Catal 2004, 346, 1553–1582.
[4] (a) Dupont, J.; Pfeffer, M.; Spencer, J. Eur J Inorg
Chem 2001, 1917–1927; (b) Herrmann, W. A. Angew
Chem, Int Ed 2002, 41, 1290–1309; (c) van der Boom,
M. E.; Milstein, D. Chem Rev 2003, 103, 1759–1792;
(d) Bedford, R. B. Chem Commun 2003, 1787–1797;
This compound was prepared from 1,3-bis(2-
thiophenemethyl)aminopropane (4.42 g, 16.58 mmol)
CH(OEt)3 (5 mL) and NH4PF6 (2.70 g, 16.56 mmol)
1
Yield: 6.1 g, 87%, mp 171–172◦C. H NMR (DMSO)
δ: 1.88 (quin., 4H, J = 6 Hz, NCH2CH CH2N), 3.27
2
Heteroatom Chemistry DOI 10.1002/hc