PAPER
Synthesis and Catalytic Applications of Di(1-adamantyl)alkylphosphines
939
3
2
7.0 (d, 2JC,P = 4.7 Hz, isobutyl-CH), 24.2 (d, J = 8.5 Hz, isobu-
Di(1-adamantyl)-2-methoxyethylphosphonium Bromide (1g)
C,P
1
tyl-CH ), 20.1 (d, J = 37.6, PCH2).
IR (KBr): 3400 (m, br), 2930 (s), 2853 (s), 2823 (m), 2682 (w),
3
C,P
–
1
+
+
1451 (m), 1345 cm (m).
MS (EI, 70 eV): m/z (%) = 358 (M , 48), 135 (Ad , 100).
1
H NMR (250 MHz, CDCl ): d = 1.80–2.21 (30 H, m, adamantyl-
3
Anal. Calcd for C H IP (486.46): C, 59.26; H, 8.23. Found: C,
24
40
3
(
0H), 2.58–2.69 (2 H, m, P-CH ), 3.41 (3 H, s, OCH ), 3.75–3.91
2
3
5
9.42; H, 8.33.
1
2 H, m, OCH ), 7.31 (1 H, d, J = 472.8 Hz, PH).
2 H,P
1
3
2
Di(1-adamantyl)allylphosphonium Bromide (1c)
C NMR (62 MHz, CDCl ): d = 66.6 (d, J = 4.7 Hz, OCH ),
2 1
3
C,P
2
IR (KBr): 3420 (s, br), 2904 (s), 2852 (s), 2682 (w), 2301 (w), 1634
59.1 (OCH ), 38.2 (d, J = 2.8 Hz, C-2), 37.4 (d, J = 31.9 Hz,
3 C,P C,P
C-1), 35.6 (d, J = 1.9 Hz, C-4), 27.5 (d, J = 9.4 Hz, C-3), 14.4
(d, JC,P = 42.4 Hz, PCH
MS (EI, 70 eV): m/z (%) = 360 (M , 16), 135 (Ad , 100).
Anal. Calcd for C H BrOP (441.43): C, 62.58; H, 8.62. Found: C,
w), 1451 cm–1 (m).
4
3
(
C,P C,P
1
1
2
).
H NMR (250 MHz, CDCl ): d = 1.77–2.33 (30 H, m, adamantyl-
3
+
+
3
0H), 3.11–3.21 (2 H, m, PCH ), 5.34–5.49 (2 H, m, allyl-CH ),
2
2
1
5
.91–6.10 (1 H, m, allyl-CH), 8.0 (1 H, dt, JH,P = 481.9 Hz,
3
23 38
JH,H = 4.0 Hz, PH).
6
2.50; H, 8.72.
1
3
2
C NMR (62 MHz, CDCl ): d = 126.9 (d, J = 8.5 Hz, allyl-CH),
3
C,P
3
2
1
3
3
23.0 (d, J = 12.2 Hz, allyl-CH ), 38.3 (d, J = 2.8 Hz, C-2),
7.9 (d, J = 31.0 Hz, C-1), 35.4 (C-4), 27.4 (d, J = 9.4 Hz, C-
), 18.6 (d, J = 39.5 Hz, PCH2).
Di(1-adamantyl)-3-chloropropylphosphonium Iodide (1h)
IR (KBr): 3420 (s, br), 2914 (s) 2853 (s), 2284 (m), 1453 (m), 1343
cm (m).
C,P
2
C,P
3
1
C,P
1
C,P
–1
C,P
+
+
1
MS (EI, 70 eV): m/z (%) = 342 (M , 30.6), 135 (Ad , 100).
H NMR (250 MHz, CDCl ): d = 1.75–2.41 (34 H, m, adamantyl-
3
3
3
0H, 3-chloropropyl-4H), 3.79 (2 H, t, J = 5.18 Hz, 3-chloropro-
Anal. Calcd for C H BrP (423.42): C, 65.25; H, 8.51. Found: C,
23
36
1
pyl-CH ), 7.88 (1 H, d, J = 468.5 Hz, PH).
1
2
H,P
6
5.12; H, 8.51.
3
3
C NMR (62 MHz, CDCl ): d = 45.3 (d, J = 12.2 Hz, 3-chloro-
3
C,P
2
1
Di(1-adamantyl)benzylphosphonium Bromide (1d)
IR (KBr): 3420 (s, br), 2903 (s) 2852 (s), 2796 (w), 2224 (m), 1497
propyl-g-CH ), 37.9 (d, J = 1.9 Hz, C-2), 37.9 (d, J = 31.9
2 C,P C,P
2
Hz, C-1), 35.6 (C-4), 29.1 (d, J = 4.7 Hz, 3-chloropropyl-b-
C,P
m), 1347 cm–1 (m).
CH ), 27.5 (d, J = 9.4 Hz, C-3), 9.1 (d, J = 40.4 Hz, 3-chloro-
3
1
(
2
C,P
C,P
1
propyl-a-CH ).
2
H NMR (250 MHz, CDCl ): d = 1.7–2.29 (30 H, m, adamantyl-H),
3
+
+
3
.67–3.76 (2 H, m, PCH ), 7.34–7.4 (3 H, m, aromatic-3H), 7.63 (2
MS (EI, 70 eV): m/z (%) = 378 (M , 35.5), 135(Ad , 100).
2
3
1
H, d, J = 7.9 Hz, aromatic-2H), 8.2 (1 H, dt, J = 480.4 Hz,
H,H
H,P
Anal. Calcd for C H ClIP (506.88): C, 54.49; H, 7.31. Found: C,
3
1
27 37
JH,H = 6.1 Hz, PH).
5
4.06; H, 7.37.
3
2
C NMR (62 MHz, CDCl ): d = 130.3 (d, J = 7.5 Hz, aromatic
3
C,P
C), 130.1 (d, JC,P = 6.0 Hz, 2 aromatic CH), 129.5 (d, J = 1.5 Hz,
Phosphines from Phosphonium Salts; General Procedure
Phosphonium salt (2.2 mmol) was added to a cooled solution (–
C,P
5
2
aromatic CH), 128.2 (d, J = 2.3 Hz, aromatic CH), 38.3 (d,
C,P
1
2
JC,P = 30.8 Hz, C-1), 38.1 (d, JC,P = 2.8 Hz, C-2), 35.5 (d,
78 °C) of Et N (4.44 g, 44 mmol) in di-n-butyl ether (20 mL). The
3
4
1
JC,P = 1.9 Hz, C-4), 27.6 (d, 3J = 9.4 Hz, C-3), 19.6 (d,
reaction mixture was stirred at –78 °C for 5 h and then allowed to
warm gradually to r.t. The solvent was removed under vacuum and
the residue was dissolved in degassed EtOH (5 mL). After stirring
for 15 min, the solid was filtered off and dried to yield the desired
phosphine, which can be further purified by crystallization from
EtOH.
C,P
JC,P = 36.6 Hz, PCH2).
+
+
MS (EI, 70 eV): m/z (%) = 392 (M , 25.8), 135 (Ad , 100).
Di(1-adamantyl)methylphosphonium Iodide (1e)
IR (KBr): 3410 (s, br), 2908 (s) 2851 (s), 2802 (w), 2320 (w), 1452
(
1
m), 1345 cm–1 (m).
Di(1-adamantyl)-n-butylphosphine (2a)
Mp 108–110 °C.
H NMR (250 MHz, CDCl ): d = 1.75–2.30 (33 H, m, adamantyl-
3
1
3
3
1
0H, PCH ), 7.45 (1 H, dq, J = 473.7 Hz, J = 5.9 Hz, PH).
3 H,P H,H
IR (KBr): 3425 (m, br), 2952 (s), 2847 (s), 2847 (s), 2675 (w), 1446
3
2
C NMR (62 MHz, CDCl ): d = 37.9 (d, J = 1.8 Hz, C-2), 36.0
–1
3
C,P
cm (m).
1
3
(
–
d, J = 34.8 Hz, C-1), 35.5 (C-4), 27.3 (d, JC,P = 9.4 Hz, C-3),
3.8 (d, J = 47.0 Hz, PCH3).
C,P
1H NMR (250 MHz, C
3
1
6
D
6
): d = 0.96 (3 H, t, JH,H = 7.3 Hz, CH
3
),
C,P
1
.35–2.03 (36 H, m, adamantyl-30H, butyl-6H).
+
+
MS (EI, 70 eV): m/z (%) = 316 (M , 43.5), 135 (Ad , 100).
1
3
2
C NMR (62 MHz, C D ): d = 41.3 (d, J = 11.3 Hz, C-2), 37.4
6
6
C,P
Anal. Calcd for C H IP (444.38): C, 56.75; H, 7.65. Found: C,
5
1
1
21
34
(C-4), 36.1 (d, J = 23.5 Hz, C-1), 33.9 (d, J = 26.2 Hz, butyl-
C,P C,P
6.58; H, 7.76.
3
2
a-CH ), 29.1 (d, J = 7.6 Hz, C-3), 24.9 (d, J = 13.1 Hz, butyl-
2
C,P
C,P
3
b-CH ), 17.1 (d, J = 21.6 Hz, butyl-g-CH ), 14.3 (butyl-CH ).
2
C,P
2
3
Di(1-adamantyl)isopropylphosphonium Iodide (1f)
IR (KBr): 3420 (m, br), 2909 (s) 2851 (s), 2676 (w), 2268 (w), 1454
(
1
3
+
+
MS (EI, 70 eV): m/z (%) = 358 (M , 60), 135 (Ad , 100).
m), 1342 cm–1 (m).
Di(1-adamantyl)isobutylphosphine (2b)
Mp 150–152 °C.
3
H NMR (250 MHz, CDCl ): d = 1.63 (6 H, dd, J = 7.3 Hz,
3
H,H
J
= 15.9 Hz, 2 CH ), 1.74–2.30 (30 H, m, adamantyl-30H),
.90–3.10 (1 H, m, PCH), 7.62 (1 H, d, J = 465.1 Hz, PH).
P,H
3
1
IR (KBr): 3420 (m, br), 2947 (s), 2908 (s), 2886 (s), 2847 (s), 2677
2
1
H,P
–1
(
w), 1448 (m), 1344 cm (m).
1H NMR (250 MHz, C
): d = 1.10 (6 H d, JH,H = 6.4 Hz, 2 isobu-
tyl-CH ), 1.20–1.30 (2 H, m, isobutyl-H), 1.60–2.00 (31 H, m, ada-
mantyl-30H, isobutyl-1H).
3
1
C NMR (62 MHz, CDCl ): d = 40.3 (d, J = 29.1 Hz, C-1), 38.8
3
C,P
3
2
4
D
6 6
(
d, JC,P = 2.8 Hz, C-2), 35.5 (d, JC,P = 1.8 Hz, C-4), 27.6 (d,
J
d, J = 3.7 Hz, isopropyl-CH3).
3
1
3
= 9.4 Hz, C-3), 20.2 (d, J = 34.8 Hz, isopropyl-CH), 20.2
C,P
2
C,P
(
C,P
1
3
2
+
+
C NMR (62 MHz, C
6
D
6
): d = 41.3 (d, JC,P = 11.3 Hz, C-2), 37.4
MS (EI, 70 eV): m/z (%) = 344 (M , 33.8), 135 (Ad , 100).
1
2
(
C-4), 36.1 (d, J = 23.5 Hz, C-1), 29.5 (d, J = 23.0 Hz, isobu-
C,P
3
C,P
Anal. Calcd for C H IP (472.43): C, 58.47; H, 8.05. Found: C,
5
1
23
38
tyl-CH), 29.1 (d, JC,P = 7.5 Hz, C-3), 27.4 (d, JC,P = 22.6 Hz,
8.92; H, 8.16.
3
PCH ), 24.2 (d, J = 9.4 Hz, 2 isobutyl-CH3).
2
C,P
Synthesis 2004, No. 6, 935–941 © Thieme Stuttgart · New York