Full Paper
31.77 (s, CH3), 31.45 (s, CH2), 30.99 (s, CH2), 30.90 (s, CH3) ppm.
quat Ar), 131.4 (d, J = 2.9 Hz, quat Ar), 129.02 (s, CH Ar), 128.1 (s,
CH Ar), 128.0 (s, CH Ar), 127. 8 (s, Ar CH), 127.7 (s, Ar CH), 127.1 (s,
31P NMR (202 MHz, CDCl3): δ = 41.3 ppm. HRMS (ESI–): calcd. for
C90H93Fe2O4P2S2 [M – H] 1475.4689; found 1475.4765. [α]2D0 = +15.0 CH Ar), 126.3 (s, CH Ar), 126.25 (s, CH Ar), 126.12 (s, CH Ar), 125.8
(CHCl3, c = 0.5).
(s, CH Ar), 125.6 (s, CH Ar), 125.5 (s, CH Ar), 89.00 (d, J = 24.2 Hz,
quat Cp), 72.4 (d, J = 3.7 Hz, subst Cp), 71.3 (d, J = 3.7 Hz, subst
Cp), 70.9 (d, J = 11.2 Hz, CH2), 70.7 (s, subst Cp), 69.7 (s, subst Cp),
69.6 (s, Cp), 34.4 (C-CH3), 34.3 (C-CH3), 34.2 (s, CH2), 34.0 (s, CH2),
33.6 (s, CH2), 31.7 (s, CH3), 31.6 (s, CH3), 31.5 (s, CH3) ppm. 31P NMR
(202 MHz, CDCl3): δ = –22.2 ppm.
Synthesis of (4-tert-Butylphenyl) (S)-[(2-Diphenylthiophos-
phinoferrocenyl)methyl] Oxide: In a Schlenk tube under argon,
a mixture of 4-tert-butylphenol (0.616 mmol), triphenylphosphine
(0.992 mmol), and (S)-(2-diphenylthiophosphinoferrocenyl)meth-
anol (0.308 mmol) was dissolved in THF (48 mL) and then cooled
in an ice bath. At this temperature, diethyl diazodicarboxylate (40 %
in toluene, 1.317 mmol) was added dropwise, and the resulting
mixture was stirred at room temperature for 12 h. The solvent was
removed in vacuo, and the crude product was purified by flash
chromatography on a silica gel column (EtOAc/hexanes, 1:10) to
give the product (82 % yield) as an orange solid. 1H NMR (400 MHz,
CDCl3): δ = 7.85 (m, 2 H, PPh2), 7.66 (m, 2 H, PPh2), 7.49 (m, 2 H,
PPh2), 7.34 (m, 4 H, PPh2), 7.21 (m, 2 H, O-C6H4-p-tBu), 6.64 (m, 2 H,
O-C6H4-p-tBu), 5.05 [d (AB system), J = 11.1 Hz, 1 H, CH2], 5.02 [d
(AB system), J = 11.1 Hz, 1 H, CH2], 4.75 (br. s, 1 H, subst Cp), 4.40
(br. s, 1 H, subst Cp), 4.39 (s, 5 H, unsubst Cp), 3.95 (br. s, 1 H, subst
Cp), 1.29 [s, 9 H, C(CH3)3] ppm. 13C NMR (300 MHz, CDCl3): δ = 159.3
(quat Ar C-O-CH2), 143.2 (quat Ar C-O-tBu), 133.8 (d, 1JC,P = 19.4 Hz,
quat Ar C-P), 132.2 (d, 3JC,P = 10.8 Hz, PhH), 132.0 (d, 3JC,P = 10.7 Hz,
5,11,17,23-Tetra-tert-butyl-25-(S)-(2-diphenylphosphinoferro-
cenyl)methoxy-27-benzyloxy-26,28-calix[4]arene [(S)-7]: (87 %
yield). 1H NMR (400 MHz, CDCl3): δ = 7.69 (m, 2 H, Ar), 7.55 (m, 3
H, Ar), 7.4 (m, 6 H, ArH, 2 OH), 7.14 (m, 8 H, ArH), 7.03 (m, 2 H, Ar),
6.77 (m, 3 H, Ar), 6.70 (br. s, 1 H, Ar), 5.23 (br. s, 1 H, subst Cp), 5.17
[d (AB system), J = 11.8 Hz, 1 H, CH2], 5.06 [dd (AB system), J =
11.4 Hz, 2 H, PhCH2O], 4.52 [d (AB system), J = 12.8 Hz, 1 H, CH2],
4.52 [d (AB system), J = 12.9 Hz, 1 H, CH2], 4.40 (br. s, 1 H, subst
Cp), 4.38 (d, J = 13.5 Hz, 2 H, CH2), 4.36 (br. s, 1 H, subst Cp), 4.19
(s, 5 H, Cp), 4.16 [d (AB system), J = 13.3 Hz, 1 H, CH2], 3.43 [d (AB
system), J = 13.6 Hz, 1 H, CH2], 3.36 [d (AB system), J = 13.8 Hz, 1
H, CH2], 3.34 [d (AB system), J = 13.8 Hz, 1 H, CH2], 3.14 [d (AB
system), J = 13.2 Hz, 1 H, CH2], 1.35 (s, 9 H, tBu), 1.33 (s, 9 H, tBu),
0.94 (s, 9 H, tBu), 0.92 (s, 9 H, tBu) ppm. 13C NMR (400 MHz, CDCl3):
δ = 150.9 (s, quat Ar C-CH2), 150.8 (s, quat Ar C-CH2), 149.9 (s, quat
Ar C-OCH2), 149.8 (s, quat Ar C-OH), 146.9 (s, quat Ar C-tBu), 146.8
(s, quat Ar C-tBu), 141.3 (s, quat Ar C-tBu), 141.2 (s, quat Ar C-tBu),
137.2 (s, quat Ar C-OCH2), 134.9 (d, J = 20.5 Hz, quat Ar PPh2), 132.4
(d, J = 24.3 Hz, quat Ar PPh2), 129.2 (s, quat Ar C-CH2), 129.1 (s, quat
Ar C-CH2), 128.9 (s, quat Ar C-CH2), 128.6 (s, Ar CH), 128.3 (s, Ar CH),
128.2 (s, Ar CH), 128.1 (s, Ar CH), 127.92 (s, Ar CH), 127.89 (s, Ar CH),
127.85 (s, quat Ar C-CH2), 127.78 (s, quat Ar C-CH2), 127.77 (s, Ar
CH), 127.59 (s, quat Ar C-CH2), 127.43 (s, quat Ar C-CH2), 125.5 (s, Ar
CH), 125.46 (s, Ar CH), 125.3 (s, Ar CH), 125.2 (s, Ar CH), 125.05 (s, Ar
CH), 125.02 (s, Ar CH), 124.99 (s, Ar CH), 124.86 (s, Ar CH), 89.68 (d,
J = 22.7 Hz, quat Cp), 78.3 (s, PhCH2O), 73.5 (d, J = 12.5 Hz, subst
Cp), 70.95 (d, J = 3.7 Hz, quat Cp), 70.2 (d, J = 3.7 Hz, subst Cp),
70.0 (s, 5 C, CH Cp), 69.7 (subst Cp), 69.6 (s, CH2), 53.4 (CH2), 33.90
(C-CH3), 33.86 (C-CH3), 33.83 (C-CH3), 31.77 (s, CH3), 31.75 (s, CH3 +
CH2), 31.50 (s, CH2), 31.48 (s, CH2), 31.24 (s, CH2), 30.98 (s, CH3),
30.96 (s, CH3) ppm. 31P NMR (400 MHz, CDCl3): δ = –23.0 ppm.
4
4
PhH), 131.3 (d, JC,P = 2.9 Hz, PhH), 131.1 (d, JC,P = 2.9 Hz, PhH),
2
2
128.2 (d, JC,P = 11.2 Hz, PhH), 128.0 (d, JC,P = 11.2 Hz, PhH), 125.9
(ArH), 114.1 (ArH), 87.5 (d, J = 11.7 Hz, quat Cp), 75.11 (d, J = 12.6 Hz,
subst Cp), 73.78 (d, J = 9.2 Hz, subst Cp), 70.8 (s, Cp), 75.0 (d, J =
94.6 Hz, quat Cp), 69.7 (d, J = 10.4 Hz, subst Cp), 64.7 (s, CH2), 34.0
[C(CH3)3], 31.5 [C(CH3)3] ppm. 31P NMR (202 MHz, CDCl3): δ =
41.7 ppm. HRMS (ESI–): calcd. for C33H33FeOPSNa [M + Na] 587.1237;
found 587.1245 (25 %); calcd. for C23H20FePS [M – (OAr)] 415.0373;
found 415.0378 (100 %). [α]2D0 = +36.1 (CHCl3, c = 0.4).
General Procedure of Desulfuration of the Thiophosphines: In
a Schlenk tube, the thiophosphine derivative (0.115 mmol) was dis-
solved in toluene (5 mL) along with tris(dimethylamino)phosphine
(0.2 mL) under argon. The resulting solution was heated at reflux
overnight. After the mixture was cooled to room temp., the solvent
was removed in vacuo. The crude product was purified by flash
chromatography under argon on a silica gel column (CH2Cl2) to give
the product as an orange solid.
5,11,17,23-Tetra-tert-butyl-25,27-bis[(S)-(2-diphenylphosphino-
ferrocenyl)methoxy]-26,28-calix[4]arene [(S,S)-8]: (92 % yield).
1H NMR (400 MHz, CDCl3): δ = 7.56 (m, 4 H, Ar), 7.40 (m, 6 H, Ar),
7.22–7.06 (m, 12 H, Ar), 7.00 (d, J = 2.2 Hz, 2 H, Ar), 6.97 (br. s, 2 H,
OH), 6.69 (d, J = 2.2 Hz, 2 H, Ar), 6.62 (d, J = 2.2 Hz, 2 H, Ar), 5.25
(br. s, 2 H, subst Cp), 5.49 [d (AB system), J = 11.9 Hz, 2 H, CH2],
5,11,17,23-Tetra-tert-butyl-25-(S)-(2-diphenylphosphinoferro-
cenyl)methoxy-26,27,28-calix[4]arene [(S)-6]: (90 % yield). 1H
NMR (500 MHz, CDCl3): δ = 7.50 (m, 2 H, Ar), 7.36 (m, 3 H, 2 OH,
Ar), 7.30 (m, 2 H, Ar), 7.26 (m, 1 H, Ar), 7.18 (m, 2 H, Ar), 7.15 (m, 1 4.62 [d (AB system), J = 11.3 Hz, 2 H, CH2], 4.55 [d (AB system), J =
H, Ar), 7.10 (m, 1 H, Ar), 7.08 (m, 1 H, Ar), 7.05 (m, 1 H, Ar), 7.00 (m,
3 H, Ar), 7.00 (br. s, 1 H, OH), 6.87 (m, 1 H, Ar), 6.77 (m, 2 H, Ar),
12.6 Hz, 2 H, CH2], 4.39 (m, 2 H, subst Cp), 4.24 (s, 10 H, Cp), 4.05
[d (AB system), J = 13.1 Hz, 2 H, CH2], 3.77 (m, 2 H, subst Cp), 3.42
4.69 [d (AB system), J = 14.6 Hz, 1 H, CH2], 4.62 (m, 2 H, CH2), 4.58 [d (AB system), J = 13.0 Hz, 2 H, CH2], 3.07 [d (AB system), J =
(m, 1 H, subst Cp), 4.31 [td (AB system), J = 12.6 Hz, 3 H, CH2], 4.23
(m, 2 H, CH2), 3.94 (s, 5 H, Cp), 3.66 [d (AB system), J = 14.5 Hz, 2
H, CH2], 3.65 [d (AB system), J = 14.4 Hz, 1 H, CH2], 3.61 (br. s, 1 H,
subst Cp), 1.42 (s, 9 H, tBu), 1.39 (s, 9 H, tBu), 1.29 (s, 9 H, tBu), 1.17
(s, 9 H, tBu) ppm. 13C NMR (300 MHz, CDCl3): δ = 154.8 (s, quat Ar
C-OH), 147.08 (s, quat Ar C-OCH2), 147.05 (s, quat Ar C-OH + quat
13.2 Hz, 2 H, CH2], 1.35 (s, 18 H, tBu), 0.86 (s, 18 H, tBu) ppm. 13C
NMR (400 MHz, CDCl3): δ = 150.8 (s, quat Ar C-OCH2), 149.9 (s, quat
Ar C-OH), 146.7 (s, quat Ar C-tBu), 141.1 (s, quat Ar C-tBu), 139.1 (d,
J = 9.8 Hz, quat Ar PPh2), 137.1 (d, J = 9.2 Hz, quat Ar PPh2), 135.1
(s, Ar CH), 134.9 (s, Ar CH), 132.23 (s, quat Ar C-CH2), 132.21 (s, Ar
CH), 132.03 (s, quat Ar C-CH2), 132.01 (s, quat Ar C-CH2), 129.1 (s,
Ar C-tBu), 147.6 (s, quat Ar C-OH), 146.5 (s, quat Ar C-tBu), 146.2 (s, CH Ar), 128.7 (d, J = 86.0 Hz, quat Ar PPh2), 128.24 (d, J = 9.8 Hz,
quat Ar C-tBu), 145.9 (s, quat Ar C-tBu), 144.4 (s, Ar CH), 138.9 (d,
J = 8.8 Hz, quat Ar PPh2), 137.4 (d, J = 8.8 Hz, quat Ar PPh2), 135.3
(s, Ar CH), 135.1 (s, Ar CH), 134.9 (d, J = 3.7 Hz, CH Ar PPh2), 134.8
(d, J = 3.7 Hz, CH Ar PPh2), 133.3 (s, quat Ar C-CH2), 133.28 (s, Ar
CH Ar PPh2), 128.17 (d, J = 11.4 Hz, CH Ar PPh2), 127.9 (s, s, quat Ar
C-CH2), 127.7 (d, J = 22.8 Hz, CH Ar PPh2), 125.29 (s, Ar CH), 125.18
(s, quat Ar C-CH2), 124.98 (s, Ar CH), 124.89 (s, Ar CH), 89.47 (d, J =
23.2 Hz, quat Cp), 74.63 (d, J = 7.4 Hz, subst Cp), 73.72 (s, CH2),
CH), 133.22 (s, quat Ar C-CH2), 132.94 (s, quat Ar C-CH2), 132.91 (s, 73.60 (s, CH2), 71.08 (d, J = 3.4 Hz, subst Cp), 70.91 (d, J = 3.5 Hz,
quat Ar C-CH2), 131.8 (s, CH Ar), 131.6 (s, CH Ar), 130.4 (d, J = 2.9 Hz,
subst Cp), 70.06 (s, Cp), 69.66 (s, subst Cp), 33.82 (C-CH3), 33.78 (C-
Eur. J. Org. Chem. 0000, 0–0
6
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim