BelØn Martín-Matute et al.
FULL PAPERS
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22.6 Hz, CHo PPh2), 132.96 (d, 2JCP =19.8 Hz, CHo PPh2),
(52%). H NMR (CDCl3, 300 MHz): d=4.63 (m, 1H), 4.44
(dd, J=1.7, 1.9 Hz, 2H), 4.39–4.33 (m, 5H), 4.31 (d, J=
1.7 Hz, 1H), 3.66 (t, J=6.6 Hz, 2H), 3.43 (t, J=6.6 Hz, 2H),
1.58–1.49 (m, 4H), 1.40–1.25 (m, 4H), 1.12 (s, 9H), 1.09–
1.01 (m, 21H); 13C NMR (CDCl3, 75 MHz): d=86.07, 71.45,
71.09, 70.44, 70.38, 70.34, 70.31, 69.89, 68.40, 65.95, 63.42,
54.99, 32.99, 29.76, 26.03, 25.69, 22.78 (3C), 18.05 (6C), 11.99
(3C); EI-MS (70 EV): m/z (%)=576 (15) [M+], 520 (30),
476 (5), 329 (10), 303 (5), 246 (100), 196 (11), 131 (50), 83
(61); HPLC conditions: AS-H column (Chiral Daicel);
0.5 mLminÀ1; 95:5 (hexane:2-propanol): (S): 6.4 min, (R):
7.2 min.
3
129.17 (CHp PPh2), 128.19 (CHp PPh2), 128.04 (d, JCP
=
7.2 Hz, PPh2), 127.96 (d, 3JCP =9.9 Hz, PPh2), 91.39, 83.47,
2
3
83.03, 81.28 (d, JCP =5.5 Hz, C5H3), 80.32 (d, JCP =2.2 Hz,
C5H3), 73.36, 71.83, 70.49 (d, 1JCP =12.6 Hz, C5H3), 70.02,
68.11, 59.59, 46.70, 31.06 (3C); 31P NMR (121.5 MHz,
CDCl3): d=À26.50; EI-MS (70 EV): m/z (%)=488
C
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19.32 min. The structure was confirmed by H-13C (HMQC)
correlations.
[1-tert-Butylsulphenyl-2-triisopropylsilyl]ferrocenyl-1’-
methyl Diphenylphosphinate (9)
Ferrocene (R)-10
To a solution of (R)-12 (500 mg, 0.87 mmol) in dry THF
(20 mL) was slowly added t-BuLi (765 mL, 1.3 mmol, 1.7m in
pentane) at À788C under a nitrogen atmosphere. The mix-
ture was stirred for 20 min at À788C before adding diphe-
nylphosphine chloride (287 mg, 1.3 mmol). The mixture was
stirred for 3 h at À788C. After evaporation of the solvent
the mixture was dissolved in dry toluene (16 mL). Then
Et3N (876 mg, 8.67 mmol) and Cl3SiH (1.7 g, 13 mmol) were
added at room temperature under a nitrogen atmosphere.
The reaction mixture was left stirring under reflux over-
night. The flask was cooled to room temperature and a 1N
solution of NaOH (20 mL) was added. The organic phase
was washed with brine and (R)-10 was isolated by flash
chromatography (SiO2, hexane/EtOAc, 3:1) as a dark brown
oil; yield: 421 mg (65%). Alcohol 13 (ca. 4%) and dimer 14
(17%) were also formed in this transformation.
When the ortho-lithiated intermediate formed from (R)-5 is
left at À788C for prolonged reaction times (1 h) before
adding Ph2PCl, a retro-Brook rearrangement of the silyl
1
groupgives rise to the formation of ferrocene 9. H NMR
(CDCl3, 300 MHz): d=7.90–7.80 (m, 4H), 7.49–7.41 (m,
6H), 4.77–4.76 (dd, J=1, 1.1 Hz, 1H), 4.48–4.45 (m, 2H),
4.41–4.30 (m, 4H), 4.24 (dd, J=1, 1.1 Hz, 1H), 4.08 (dd, J=
2.7, 3.1 Hz, 1H), 1.06 (m, 21H), 0.89 (s, 9H); 13C NMR
(CDCl3, 75 MHz): d=135.08 [d, 1JCP =9.9 Hz, Cipso
1
P(O)Ph2], 133.67 [d, JCP =8.8 Hz, Cipso P(O)Ph2], 132.09 [d,
2JCP =9.3 Hz, CHo P(O)Ph2], 131.67 [d, 2JCP =9.3 Hz, CHo
P(O)Ph2], 131.24 [CHp P(O)Ph2], 128.07 [d, 3JCP =3.3 Hz,
CHm P(O)Ph2], 127.91 [d, 3JCP =3.8 Hz, CHm P(O)Ph2],
90.79, 81.98–75.20 (several peaks overlapping), 72.81 (d,
3JCP =2.2 Hz, C5H4), 72.68, 71.53, 71.34, 69.19, 60.63, 46.27,
31.02 (3C), 18.09 (6C), 12.00 (3C) [one C signal for CHp
P(O)Ph2] is missing due to overlapping); 31P NMR
(121.5 MHz, CDCl3): d=+25.03; EI-MS (70 EV): m/z
(%)=660 (19) [M+], 526 (100), 483 (32), 449 (7), 397 (11),
352 (85), 228 (8).
(R)-10: 1H NMR (CDCl3, 300 MHz): d=7.60–7.55 (m,
2H), 7.37–7.22 (m, 5H), 7.15–7.14 (m, 3H), 4.56 (d, J=
1.3 Hz, 1H), 4.38 (t, J=2.5 Hz, 1H), 4.14–4.13 (m, 1H), 4.06
(dd, J=1.3, 2.5 Hz, 1H), 3.96–3.97 (m, 1H), 3.92 (s, 1H),
3.86–3.85 (m, 1H), 3.80 (d, J=1,1 Hz, 1H), 3.73 (s, 1H),
3.58 (t, J=6.5 Hz, 2H), 3.21 (t, J=6.5 Hz, 2H), 1.50–1.40
6-Triisopropylsilyloxy-1-hexanol (11)
(m, 3H), 1.25–1.19 (m, 4H), 1.12–1.10 (m, 21H), 0.92 (s,
1
9H); 13C NMR (CDCl3, 75 MHz): d=140.12 (d, JCP
=
To a solution of 1-bromo-6-hexanol (100 mg, 0.55 mmol)
and imidazole (56 mg, 0.83 mmol) in dry CH2Cl2 (1.4 mL)
was added triisopropylsilyl chloride (116 mg, 0.60 mmol) at
room temperature under a nitrogen atmosphere. The result-
ing mixture was stirred at room temperature overnight. The
residue was washed with H2O (4) and extracted with
CH2Cl2. The solvent was removed under reduced pressure
and the residue was purified by flash chromatography (SiO2,
hexane/EtOAc, 3:1) affording 11 as a colourless; yield:
9.9 Hz, Cipso PPh2), 138.40 (d, 1JCP =9.4 Hz, CHipso PPh2),
2
135.37 (d, 2JCP =22.6 Hz, CHo PPh2), 132.87 (d, JCP
=
=
3
19.3 Hz, CHo PPh2), 129.12 (CHp PPh2), 128.13 (d, JCP
7.7 Hz, CHm PPh2), 127.89 (d, 3JCP =6.6 Hz, CHm PPh2),
2
3
85.27, 84.02, 81.11 (d, JCP =5.5 Hz, C5H3), 80.70 (d, JCP
=
=
2
3
2.2 Hz, C5H3), 73.60 (d, JCP =4.9 Hz, C5H3), 72.18 (d, JCP
3.8 Hz, C5H3), 71.80, 71.47, 71.06, 71.04, 67.98, 63.41, 40.07,
32.98, 31.10 (3C), 29.70, 25.99, 25.68, 18.04 (6C), 12.01 (3C)
(two peaks are missing due to overlapping); EI-MS (70
EV): m/z (%)=760 (39) [M+ +16], 717 (10), 626 (78), 430
(15), 352 (100), 298 (5), 229 (7), 201 (12), 131 (32), 83 (39).
13: 1H NMR (CDCl3, 300 MHz): d=4.57 (dd, J=1.1,
1.2 Hz, 1H), 4.37–4.23 (m, 9H), 3.56 (t, J=6.6 Hz, 2H), 3.37
(dt, J=3.4, 6.5 Hz, 2H), 2.35 (s, OH), 1.54–1.26 (m, 8H),
1.06 (s, 9H); 13C NMR (CDCl3, 75 MHz): d=84.66, 76.60
(2C), 76.25, 70.81 (2C), 70.13 (2C), 69.92 (2C), 68.69, 62.88,
53.40, 44.93, 32.70, 30.65 (3C), 29.64, 25.95, 25.53. EI-MS (70
EV): m/z (%)=420 (16) [M+], 364 (17), 246 (100), 198 (10),
171 (15), 121 (6).
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104 mg (69%). H NMR (CDCl3, 300 MHz): d=3.66 (t, J=
6.4 Hz, 2H), 3.60 (t, J=6.6 Hz, 2H), 2.19 (s, OH), 1.55–1.35
(m, 8H), 1.04–1.03 (m, 21H).
Ferrocene (R)-12
To a solution of (R)-4 (200 mg, 0.63 mmol) in dry CH2Cl2
(1.2 mL)
(1.9 mg, 0.0125 mmol) in dry Et2O (0.2 mL) was added, fol-
lowed by a solution of TiPSO(CH2)6OH (11) (343 mg,
a solution of trifluoromethanesulphonic acid
AHCTREUNG
1.25 mmol) in dry CH2Cl2 (0.8 mL) at 08C under a nitrogen
atmosphere. The reaction mixture was left stirring overnight
at room temperature. After evaporation of the solvent and
purification by flash chromatography (SiO2, hexane/EtOAc,
1:1), (R)-12 was obtained as a dark brown oil; yield: 199 mg
14: 1H NMR (CDCl3, 300 MHz): d=4.60 (dd, J=1.1,
1.2 Hz, 2H), 4.41–4.27 (m, 18H), 3.39 (t, J=3.4 Hz, 4H),
1.54–1.28 (m, 8H), 1.10 (s, 18H); 13C NMR (CDCl3,
75 MHz): d=86.10 (2C), 71.36 (2C), 71.03 (2C), 70.49 (2C),
1722
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2007, 349, 1714 – 1724