5
34
A. Marian and G. Maas: Diethyl (iodoethynyl)phosphonate and (iodoethynyl)diphenylphosphane oxide
2
5
00 MHz): δ = 1.89/2.26 (AB system, J = 6.7 Hz, 2H, 7-
HH
4.3 [3+2] Cycloaddition reactions
H ), 3.77 and 3.84 (2 s, 2H, 1,4-H), 6.60 (dd, J = 5.0,
2
2
.9 Hz, 1H, CHolefin), 6.74 (dd, J = 4.8, 3.2 Hz, 1H, CHol-
4.3.1 Diethyl (1-benzyl-5-iodo-1H-1,2,3-triazol-4-yl)
phosphonate (8a) and diethyl (1-benzyl-4-iodo-1H-
1,2,3-triazol-5-yl)phosphonate (8b)
efin), 7.33–7.40 (m, 4H, CH ), 7.40–7.46 (m, 2H, CHPh),
7
Ph
1
3
1
.52–7.58 (m, 4H, CHPh). – C{ H} NMR (CDCl , 126 MHz):
3
δ = 55.65 (d, JP,C = 10.1 Hz, C-1 or C-4), 67.47 (d,
JP,C = 10.2, C-4 or C-1), 72.53 (d, JP,C = 4.3 Hz, C-7), 122.76
A thick-walled Schlenk tube fitted with a screw cap was
purged with argon and charged with a solution of benzyl
azide (533 mg, 4.0 mmol) and alkyne 2 (1.00 g, 3.47 mmol)
in anhydrous acetonitrile (6 mL). After heating at 80 °C for
six days, the reaction mixture was brought to r. t., the
solvent was evaporated, and the residue was subjected to
column chromatography (silica gel (150 g), elution with
2
(
d, J
= 6.0 Hz, CI), 128.53 (d, JP,C = 3.5 Hz, CHPh),
P,C
1
28.63 (d, JP,C = 3.4 Hz, CHPh), 130.76 (d, JP,C = 65.0 Hz,
CPh), 131.19 (d, JP,C = 43.0 Hz, CPh), 131.77 (d,
JP,C = 7.1 Hz, CHPh), 131.85 (d, JP,C = 7.3 Hz, CHPh), 132.00
(
d, JP,C = 3.0 Hz, CHPh), 132.02 (d, JP,C = 3.0 Hz, CHPh),
1
40.10 (d, JP,C = 1.9 Hz, CH ), 142.25 (d, J = 0.6 Hz,
Ph P,C
1
31
CHPh), 148.21 (d, J = 112.4 Hz, C-2). – P NMR (CDCl ):
P,C
3
EtOAc-cyclohexane (1:1) to furnish 8b (R = 0.56) and 8a
f
δ = 25.20. – Anal. calcd. for C H IOP (418.21): C 54.57,
1
9
16
(R = 0.15).
f
H 3.86; found C 54.80, H 3.87.
Isomer 8a: yellowish solid (780 mg, 1.85 mmol, 54%
yield), m. p. 71 °C. – IR (KBr): ṽ = 2117 (s), 1456 (s), 1392 (m),
4
.2.6.5 1-(Diphenylphosphoryl)-2-iodo-3,4,5,6-tetraphe-
1261 (s), 1200 (s), 1160 (s), 1103 (s), 1017 (s), 796 (m), 724 (s)
nylbenzene (7b)
−1
1
cm . – H NMR (CDCl , 400 MHz): δ = 1.37 (td, J = 7.1, 0.5 Hz,
3
Prepared from alkyne 5 (300 mg, 0.85 mmol) and tetra-
phenyl-cyclopentadienone (610 mg, 1.5 mmol); 125 °C, four
days. R = 0.50 (CHCl -EtOAc (3:1)). Colorless solid (500 mg,
6
H, CH ), 4.17–4.31 (m, 4H, OCH ), 5.65 (s, 2 H, PhCH ),
3 2 2
13 1
7
.27–7.38 (m, 5 H, CH ). – C{ H} NMR (CDCl , 100.61 MHz):
Ph 3
f
3
δ = 16.38 (d, JPC = 6.6 Hz, CH ), 54.43 (s, PhCH ), 63.44 (d,
3
2
0
.71 mmol, 83% yield), m. p. 299 °C. – IR (KBr): ṽ = 1489 (m),
2
JPC = 5.8 Hz, OCH ), 86.24 (d, J = 34.0 Hz, CI); 128.07,
2
PC
1
437 (s), 1371 (m), 1168 (s), 1104 (m), 1072 (m), 1022 (m), 762
−
1
1
128.85, 129.08 (3 s, CH ); 133.71 (s, C ), 142.54 (d,
Ph Ph
(m) cm . – H NMR (CDCl , 400 MHz): δ = 6.52–6.85 (m,
3
1
31
JPC = 242.6 Hz, PC=). – P NMR (CDCl ): δ = 5.66. – HRMS
3
1
4
–
5H), 6.99–7.03 (m, 2H), 7.07–7.25 (m, 9H), 7.51–7.58 (m,
+
13 1
((+)-ESI): m/z = 443.9944; calcd. 443.9950 [M+Na] . – Anal.
calcd. for C H IN O P (421.1): C 37.07, H 4.07, N 9.98;
H). – C{ H} NMR: see the Supporting Information.
31
13
17
3 3
P NMR (CDCl ): δ = 31.70. – HRMS (ESI): m/z = 708.1078;
3
+
found C 37.08, H 4.11, N 10.00.
calcd. for [M+H] : 708.1079. – Anal. calcd. for C H IO P
4
2
30
3
Isomer 8b: yellowish very viscous oil (380 mg,
(708.58): C 71.19, H 4.27; found C 71.21, H 4.30.
0
.90 mmol, 26% yield). – IR (KBr): ṽ = 1456 (s), 1261 (s), 1200
4
.2.6.6 15-(Diphenylphosphoryl)-16-iodotetracyclo
−1
(
s), 1160 (s), 1103 (s), 1021 (s), 796 (s), 724 (s), 696 (m) cm .
2,7
9,14
[6.6.2.0 .8 ]hexadeca-2,4,6,9(14),10,12,15-heptaene (7c)
1
–
H NMR (CDCl , 400 MHz): δ = 1.22 (td, J = 7.1, 0.6 Hz, 6H,
3
Prepared from alkyne 5 (400 mg, 1.14 mmol) and
anthracene (445 mg, 5.5 mmol); 125 °C, 13 days. Purifica-
tion by repeated column chromatography (1. silica gel
CH ), 3.83–4.04 (m, 4H, OCH ), 5.96 (s, 2H, PhCH ), 7.28–
3
2
2
13
1
7
.39 (m, 5H, H ). – C{ H} NMR (CDCl , 101 MHz): δ = 16.12
Ph
3
(
d, JPC = 6.7 Hz, CH ), 54.68 (s, PhCH ), 63.63 (d, J = 5.4 Hz,
3 2
(
100 g), CHCl -EtOAc (3:1), R = 0.49); 2.50 g of silica gel,
2
3
f
CH ), 96.81 (d, J = 19.5 Hz, CI), 128.37 (s, C ), 128.63 (s,
C ), 128.77 (s, C ), 128.97 (d, J = 220.3 Hz, PC=), 135.22
(
z = 443.9944, calcd. 443.9950 [M+Na] . ‒ Anal. calcd. for
C H IN O P (421.1): C 37.07, H 4.07, N 9.98; found C 37.06,
2
PC
Ph
CHCl -cyclohexane (1:1), R = 0.10). Colorless solid
1
3
f
Ph
Ph
PC
(
340 mg, 0.64 mmol, 56% yield), m. p. 176 °C. – IR (KBr):
31
s, C ). – P NMR (CDCl ): δ = 12.38. – HRMS ((+)-ESI): m/
Ph
3
−
1
1
ṽ = 1195 (s), 1117 (s), 1102 (m), 749 (s) cm . – H NMR (CDCl ,
+
3
4
00 MHz): δ = 5.18 (d, J = 8.7 Hz, 1H, Hbridgehead), 5.56 (d,
13
17
3 3
J = 3.0 Hz, 1H, Hbridgehead), 6.97–7.04 (m, 6H), 7.35–7.57
H 4.13, N 9.92.
1
3
1
(
m, 12H). − C{ H} NMR (CDCl , 101 MHz): δ = 56.21 (d,
3
JP,C = 10.0 Hz, CH
), 69.53 (d, JP,C = 8.6 Hz,
bridgehead
2
CHbridgehead), 119.00 (d, J = 4.4 Hz, CI), 123.33, 123.63, 4.3.2 1-Benzyl-4-(diphenylphosphoryl)-5-iodo-1H-1,2,3-
P,C
1
25.25, 125.67, 128.69 (d, JP,C = 12.5 Hz), 130.91 (d,
triazole (9a) and 1-benzyl-5-(diphenylphosphoryl)-
4-iodo-1H-1,2,3-triazole (9b)
1
JP,C = 108.0 Hz, PCPh), 132.06 (d, JP,C = 10.3 Hz), 132.23 (d,
JP,C = 2.7 Hz), 142.56 (d, J = 2.7 Hz), 143.18 (d,
P,C
1
31
JP,C = 1.9 Hz), 144.82 (d, J = 103.7 Hz, PC=). – P NMR A thick-walled Schlenk tube fitted with a screw cap was
CDCl ): δ = 29.54. – MS (CI): m/z = 531 [M+H] . – Anal. purged with argon and charged with a solution of benzyl
calcd. for C H IOP (530.35): C 63.41, H 3.80; found C azide (100 mg, 0.8 mmol) and alkyne 5 (200 mg, 0.57 mmol)
P,C
+
(
3
2
8 20
6
3.06, H 3.87.
in anhydrous acetonitrile (4 mL). After heating at 80 °C for