RegioselectiVe Zirconophosphination of 1-Alkenes
Organometallics, Vol. 27, No. 15, 2008 3837
3
tylzirconocene generated by the reaction of Cp2ZrCl2 (1.2 mmol,
0.354 g) with 2.4 mmol of n-BuLi (1.5 mL, 1.6 M in hexane
solution) in THF (5 mL) was added 1.5 equiv of PMe3 (1.5 mL,
1.0 M in THF). The reaction mixture was kept at ambient
temperature for 1 h. Subsequently PPh2Cl (184 µL, 1.0 mmol)
was added, and the solution was stirred for 20 min at 0 °C. 31P
NMR: -15.6 (81 MHz, THF, 85% H3PO4). NMR yield is 91%.
1H NMR (300 MHz, CDCl3, Me4Si): δ 0.81 (t, JHH ) 7.5 Hz,
3H), 1.31-1.43 (m, 1H), 1.45-1.60 (m, 1H), 1.66-1.75 (m, 1H),
1.85-2.00 (m, 1H), 2.12-2.16 (m, 2H), 2.19-2.33 (m, 1H),
4.93-5.02 (m, 2H), 5.58-5.70 (m, 1H), 7.80-7.40 (m, 10H). 13
C
3
NMR (75 MHz, CDCl3, Me4Si): δ 10.6, 27.2 (d, JPC ) 7.5 Hz),
32.9 (d, 1JPC ) 71.0 Hz), 33.7 (d, 2JPC ) 2.5 Hz), 38.5 (d, 3JPC
)
3
2
9.0 Hz), 117.2, 128.7 (d, JPC ) 10.5 Hz), 130.8 (d, JPC ) 9.0
Hz), 131.6, 133.9 (d, 1JPC ) 82.5 Hz), 136.1. 31P NMR (81 MHz,
CDCl3, 85% H3PO4): δ 34.2. Positive ion ESI-MS: 299.0 (M +
H+), 321 (M + Na+). Anal. Calcd for C19H23OP: C, 76.49; H,
7.77. Found: C, 76.41; H, 7.81.
4
13C NMR (75 MHz, C6D6, Me4Si): δ 17.5 (d, JPC ) 5.0 Hz),
3
1
31.7 (d, JPC ) 5.7 Hz,), 38.7 (d, JPC ) 23.7 Hz), 60.0, 112.3,
127.9-139.1.
Preparation of Butyldiphenylphosphine 4a. The reaction
mixture containing 2-zirconobutyldiphenylphosphine 3a was quenched
by 3 M HCl and then extracted with ethyl acetate. Removing the
solvent and subsequent purification by column chromatography on
silica gel (petroleum ether) under nitrogen afforded the title
Methyl 4-((diphenylphosphoryl)methyl)-2-methylenehexanoate
5c. 1H NMR (300 MHz, CDCl3, Me4Si): δ 0.82 (t, 3JHH ) 7.5 Hz,
3H), 1.33-1.42 (m, 1H), 1.55-1.64 (m, 1H), 2.15-2.50 (m, 4H),
2
2
3.60, 5.47 (d, JHH ) 1.0 Hz, 1H), 6.17 (d, JHH ) 1.0 Hz, 1H),
1
compound as a colorless liquid in 75% isolated yield. H NMR
7.41-7.52 (m, 6H), 7.66-7.74 (m, 4H). 13C NMR (75 MHz,
3
(300 MHz, CDCl3, Me4Si): δ 0.89 (t, JHH ) 7.2 Hz, 3H),
3
1
CDCl3, Me4Si): δ 10.3, 27.2 (d, JPC ) 5.0 Hz), 32.6 (d, JPC
)
1.42-1.46 (m, 4H), 2.02-2.07 (m, 2H), 7.30-7.52 (m, 10H). 13
C
71.7 Hz), 33.4 (d, 2JPC ) 2.9 Hz), 37.2 (d, 3JPC ) 10.0 Hz), 127.2,
128.7 (d, 3JPC ) 10.8 Hz), 130.7 (d, 2JPC ) 9.0 Hz), 130.9 (d, 2JPC
) 9.0 Hz), 131.7, 132.6 (d, 1JPC ) 97.5 Hz), 138.8. 31P NMR (81
MHz, CDCl3, 85%H3PO4): δ 32.4. Positive ion ESI-MS: m/z )
357.1 (M + H+). Anal. Calcd for C21H25O3P: C, 70.77; H, 7.07.
Found: C, 70.81; H, 7.08.
NMR (75 MHz, CDCl3, Me4Si): δ 13.9, 24.4 (d, 3JPC ) 12.8 Hz),
27.9 (d, 2JPC ) 10.8 Hz), 28.2 (d, 1JPC ) 15.6 Hz), 128.5 (d, 3JPC
) 6.5 Hz), 128.5, 132.8 (d, 2JPC ) 18.8 Hz), 139.1 (d, 1JPC ) 12.8
Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ -15.6. Positive
ion ESI-MS: 243.2 (M + H+). The NMR data are consistent with
literature.19
Preparation of (2-Benzoylbutyl)diphenylphosphine Oxide
5d. After addition of CuCl (3.0 mmol, 297 mg) to the reaction
mixture of 2-zirconobutyldiphenylphosphine 3a at room tempera-
ture, benzoyl chloride (1.2 mmol, 168 mg) was added, and the
reaction mixture was stirred at room temperature for 6 h. The
resulting mixture was treated with 3 M HCl, and 30% H2O2 (2
mL) was added dropwise; the reaction mixture was stirred for 1 h.
Removing the solvent and subsequent purification by column
chromatography on silica gel (ethyl acetate/petroleum ether ) 3:1)
afforded 199 mg of the title compound as a colorless solid in 55%
isolated yield. 1H NMR (300 MHz, CDCl3, Me4Si): δ 0.79 (t, 3JHH
) 7.5 Hz, 3H), 1.60-1.69 (m, 1H), 1.73-1.85 (m, 1H), 2.30-2.46
(m, 1H), 2.97-3.08 (m, 1H), 3.96-4.07 (m, 1H), 7.24-7.84 (m,
Preparation of (2-Deuterium)butyldiphenylphosphine 4b. The
reaction was carried out in a similar way to that described above
using 20% DCl instead of 3 M HCl. The isolated yield is 75%. 1H
3
NMR (300 MHz, CDCl3, Me4Si): δ 0.87 (t, JHH ) 7.2 Hz, 3H),
1.37-1.45 (m, 2H), 1.50-1.62 (m, 1H), 2.24 (dd, 3JHH ) 8.4 Hz,
3JPH ) 10.6 Hz, 2H), 7.40-7.52 (m, 6H), 7.70-7.76 (m, 4H). 13
C
2
NMR (75 MHz, CDCl3, Me4Si): δ 13.6, 23.2 (dt, JPC ) 3.6 Hz,
3
1
1JCD ) 19.5 Hz), 24.1 (d, JPC ) 15.0 Hz), 29.5 (d, JPC ) 75.0
3
2
Hz), 128.7 (d, JPC ) 11.3 Hz), 130.9 (d, JPC ) 9.0 Hz), 131.7,
133.4 (d, JPC ) 100.5 Hz). 31P NMR (81 MHz, CDCl3, 85%
1
H3PO4): δ 35.0. Positive ion ESI-MS: 243.8 (M + H+). Anal. Calcd
for C16H18DP: C, 78.98; H, 8.28. Found: C, 79.11; H, 8.30.
Preparation of 1-(Diphenylphosphorothioyl)butane-2-thiol
5a. The reaction was carried out in a similar way. After addition
of S8 (3.0 mmol, 96 mg) to 3a at room temperature, the reaction
mixture was stirred at the same temperature for 5 h. The resulting
mixture was treated with 3 N HCl. Removing the solvent and
subsequent purification by column chromatography on silica gel
(ethyl acetate/petroleum ether ) 1:10) afforded 149 mg of the title
compound as a colorless solid. 1H NMR (300 MHz, CDCl3, Me4Si):
δ 0.86 (t, 3JHH ) 7.2 Hz, 3H), 1.53-1.68 (m, 1H), 1.79-1.90 (m,
1H), 2.33 (m, 1H), 2.70-2.87 (m, 1H), 3.05-3.24 (m, 1H),
3.40-3.60 (m, 1H), 7.40-7.50 (m, 6H), 7.83-7.89 (m, 4H). 13C
15H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 11.0, 27.6 (d, 3JPC
)
9.0 Hz), 31.0 (d, 1JPC ) 71.0 Hz), 40.5, 128.5, 128.5, 128.5, 128.7,
128.8 (d, 3JPC ) 11.3 Hz), 130.7 (d, 2JPC ) 9.0 Hz), 131.2 (d, 2JPC
1
) 9.0 Hz), 131.8, 131.9, 133.1, 133.7 (d, JPC ) 97.5 Hz), 136.4,
202.2 (d, 3JPC ) 5.6 Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4):
δ 31.7. Positive ion ESI-MS: 363.2 (M + H+), 385.1 (M + Na+).
Anal. Calcd for C23H23O2P: C, 76.23; H, 6.40. Found: C, 76.33;
H, 6.44.
4-((Diphenylphosphoryl)methyl)hexan-3-one 5e. 1H NMR (300
MHz, CDCl3, Me4Si): δ 0.83 (t, 3JHH ) 7.5 Hz, 3H), 0.84 (t, 3JHH
) 7.5 Hz, 3H), 1.34-1.45 (m, 2H), 1.52-1.59 (m, 2H), 2.17-2.27
(m, 2H), 2.97-3.14 (m, 1H), 7.39-7.49 (m, 6H), 7.66-7.74 (m,
15H). 13C NMR (75 MHz, CDCl3, Me4Si): δ 13.1, 13.7, 23.5 (d,
3
NMR (75 MHz, CDCl3, Me4Si): δ 11.3, 27.7 (d, JPC ) 6.5 Hz),
1
3
37.5 (d, JPC ) 48.8 Hz), 49.3, 128.8 (d, JPC ) 12.0 Hz), 128.8
(d, 3JPC ) 12.0 Hz), 131.0 (d, 2JPC ) 9.8 Hz), 131.3 (d, 2JPC ) 9.8
3
1
4JPC ) 3.6 Hz), 24.1 (d, JPC ) 15.1 Hz), 29.5 (d, JPC ) 71.7
1
1
Hz), 131.7, 132.7 (d, JPC ) 75.0 Hz), 133.5 (d, JPC )75.0 Hz).
31P NMR (81 MHz, CDCl3, 85% H3PO4): δ 40.2. ESI-MS: m/z )
305.0. Anal. Calcd for C16H19PS2: C, 62.71; H, 6.25. Found: C,
62.79; H, 6.26.
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3
Hz), 35.2, 128.6 (d, JPC ) 11.5 Hz), 128.7 (d, JPC ) 11.5 Hz),
130.8 (d, 2JPC ) 9.3 Hz), 131.1 (d, 2JPC ) 9.3 Hz), 133.6 (d, 1JPC
) 96.8 Hz), 211.6 (d, 3JPC ) 60.0 Hz). 31P NMR (81 MHz, CDCl3,
85% H3PO4): δ 33.3. Positive ion ESI-MS: m/z ) 315.1 (M +
H+). Anal. Calcd for C19H23O2P: C, 72.59; H, 7.37. Found: C,
72.62; H, 7.37.
Preparation of (2-Allylbutyl)diphenylphosphine Oxide 5b.
After addition of CuCl (3.0 mmol, 297 mg) to the reaction mixture
of 2-zirconobutyldiphenylphosphine at room temperature, allyl
bromide (1.2 mmol, 103 µL) was added and the reaction mixture
was stirred at room temperature for 12 h. The resulting mixture
was treated with 3 M HCl, and then 30% H2O2 (2 mL) was added
dropwise. The reaction mixture was stirred for 1.0 h. Removing
the solvent and subsequent purification by column chromatography
on silica gel (ethyl acetate/petroleum ether ) 2:1) afforded 140
mg of the title compound as a colorless solid in 47% isolated yield.
1
4-((Diphenylphosphoryl)-2-benzyl)butane 5f. H NMR (300
3
MHz, CDCl3, Me4Si): δ 0.83 (t, JHH ) 7.5 Hz, 3H), 1.39-1.43
(m, 2H), 1.53-1.57 (m, 2H), 2.17-2.20 (m, 1H), 3.06-3.13 (m,
2H), 7.02-7.13 (m, 5H), 7.34-7.50 (m, 6H), 7.60-7.73 (m, 4H).
3
13C NMR (75 MHz, CDCl3, Me4Si): δ 13.0, 18.2 (d, JPC ) 2.2
1
3
Hz), 35.7 (d, JPC ) 69.7 Hz), 37.6 (d, JPC ) 10.4 Hz), 38.4,
3
2
126.9, 128.3, 128.4, 128.6 (d, JPC ) 11.5 Hz), 131.1 (d, JPC
)
4
1
9.3 Hz), 131.8, 131.9 (d, JPC ) 2.2 Hz), 133.7 (d, JPC ) 90.3
Hz). 31P NMR (81 MHz, CDCl3, 85% H3PO4): δ 30.5. Positive
ion ESI-MS: m/z ) 349.2 (M + H+). Anal. Calcd for C23H25OP:
C, 79.29; H, 7.23. Found: C, 79.28; H, 7.24.
(19) Gordillo, B.; Dominguez, Z. J.; Sanchez, N.; Gonzalez, R.; Salas,
M.; Barragan, E. Tetrahedron Lett. 2003, 44, 5293.