Organometallics
Note
heated at 110 °C for 17−24 h. The solvent was evaporated, and the
residue was strained onto silica. Purification was performed via cold
column chromatography (0 °C) with 15/1 hexane/dichloromethane.
3c: a white solid (14 mg, 9% yield) was obtained. 31P NMR
strained onto silica. Purification was performed via cold column
chromatography (0 °C) with 15/1 hexane/dichloromethane. The yield
was 84%. The reaction was repeated in the presence of dry potassium
phosphate (260 mg, 1.2 mmol), and the yield was 45%.
1
1
(CD2Cl2): δ −27.4 (1JPW = 228.2 Hz, JPH = 348.1 Hz). H NMR
1
(CD2Cl2): δ 2.37 (s, 3H, Me), 7.03 (d, JPH = 348.1 Hz, 1H, PH),
ASSOCIATED CONTENT
* Supporting Information
Figures giving NMR spectra for compounds 3c,d,f,g. This
material is available free of charge via the Internet at http://
■
3
7.25−7.62 (m, 9H, Ar). 13C NMR (CD2Cl2): δ 21.55 (d, JCP = 6.5
S
Hz, CH3), 126.95 (d, JCP = 11.5 Hz, CH), 129.47 (d, JCP = 10.2 Hz,
CH), 131.06 (d, JCP = 2.1 Hz, CH), 131.27 (d, JCP = 1.9 Hz, CH),
131.29 (d, 1JCP = 43.6 Hz, CP), 131.65 (d, JCP = 6.8 Hz, CH), 131.76
(d, 1JCP = 42.9 Hz, CP), 133.51 (d, JCP = 12.0 Hz, CH), 133.89 (d, JCP
= 16.7 Hz, CH), 140.11 (d, 2JCP = 5.7 Hz, C-Me), 196.81 (d, 2JCP = 6.9
2
AUTHOR INFORMATION
Corresponding Author
Hz, cis CO), 199.65 (d, JCP = 21.5 Hz, trans CO). HRMS: m/z
■
524.0015 (calcd for C18H13O5PW 524.0010).
3d: a white solid (13 mg, 8% yield) was obtained. 31P NMR
1
1
(CD2Cl2): δ −60.1 (1JPW = 222.2 Hz, JPH = 345.5 Hz). H NMR
Notes
(CD2Cl2): δ 2.01 (dd, 2JPH = 8.0 Hz, 3JHH = 6.6 Hz, 3H, CH3), 2.49 (s,
1
3
The authors declare no competing financial interest.
3H, CH3), 6.03 (dq, JPH = 345.5 Hz, JHH = 6.6 Hz, 1H, PH), 7.26−
7.45 (m, 4H, Ar). 13C NMR (CD2Cl2): δ 13.43 (d, 1JCP = 29.9 Hz, P-
3
ACKNOWLEDGMENTS
The authors thank the Nanyang Technological University in
Singapore for financial support of this work.
Me), 21.03 (d, JCP = 7.2 Hz, Me), 126.97 (d, JCP = 10.2 Hz, CH),
■
130.56 (d, JCP = 2.0 Hz, CH), 130.58 (d, JCP = 29.5 Hz, CH), 131.30
(d, JCP = 6.9 Hz, CH), 132.87 (d, 1JCP = 43.3 Hz, CP), 139.15 (d, 2JCP
= 6.8 Hz, C-Me), 196.90 (d, 2JCP = 7.0 Hz, cis CO), 200.01 (d, 2JCP
=
20.3 Hz, trans CO). HRMS: m/z 461.9877 (calcd for C13H11O5PW
461.9854).
REFERENCES
■
(1) Some recent reviews: Mitchell, M. C.; Kee, T. P. Coord. Chem.
Rev. 1997, 158, 359. Trofimov, B. A.; Arbuzova, S. N.; Gusarova, N. K.
Russ. Chem. Rev. 1999, 68, 215. Alonso, F.; Beletskaya, I. P.; Yus, M.
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218. Coudray, L.; Montchamp, J.-L. Eur. J. Org. Chem. 2008, 3601. Van
der Jeught, S.; Stevens, C. V. Chem. Rev. 2009, 109, 2672. Tappe, F. M.
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R. Chem. Soc. Rev. 2012, 41, 2095. Berger, O.; Petit, C.; Deal, E. L.;
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(2) Ng, Y. X.; Mathey, F. Angew. Chem., Int. Ed. 2013, 52, 14140.
(3) Recent reviews: Slootweg, J. C.; Lammertsma, K. Sci. Synth. 2009,
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Helv. Chim. Acta 2001, 84, 2938.
3f: a white solid (46 mg, 27% yield) was obtained. 31P NMR
1
1
(CD2Cl2): δ −30.6 (1JPW = 227.7 Hz, JPH = 356.7 Hz). H NMR
3
(CD2Cl2): δ 1.36 (pseudotd, JHH = 6.8 Hz, JHH = 2.0 Hz, 3H,
1
CH3CH2O), 4.07 (m, 2H, CH3CH2O), 6.94 (pseudodd, JPH = 356.7
Hz, JHH = 2.5 Hz, 1H, PH), 6.92−7.71 (m, 9H, Ar). 13C NMR
(CD2Cl2): δ 14.62 (s, CH3CH2O), 64.49 (s, CH3CH2O), 111.76 (d,
JCP = 4.0 Hz, CH), 120.91 (d, 1JCP = 44.5 Hz, CP), 121.22 (d, JCP = 9.6
Hz, CH), 129.14 (d, JCP = 10.2 Hz, CH), 130.92 (d, JCP = 1.6 Hz,
CH), 131.25 (d, 1JCP = 44.4 Hz, CP), 132.77 (s, CH), 133.19 (d, JCP
=
8.8 Hz, CH), 133.98 (d, JCP = 11.9 Hz, CH), 159.09 (d, 2JCP = 3.2 Hz,
COCH2), 197.10 (d, 2JCP = 7.0 Hz, cis CO), 200.17 (d, 2JCP = 21.4 Hz,
trans CO). HRMS: m/z 554.0119 (calcd for C19H15O6PW 554.0116).
3g: a white solid (80 mg, 40% yield) was obtained. 31P NMR
1
1
(CD2Cl2): δ −57.3 (1JPW = 223.8 Hz, JPH = 350.2 Hz). H NMR
3
(CD2Cl2): δ 1.50 (t, JHH = 6.9 Hz, 3H, CH3CH2O), 2.00 (pseudo t,
2JPH = 6.9 Hz, 3H, CH3), 4.14 (m, 2H, CH3CH2O), 5.95 (dq, JPH
=
1
(4) Marinetti, A.; Mathey, F.; Fischer, J.; Mitschler, A. J. Am. Chem..
Soc. 1982, 104, 4484.
350.2 Hz, 3JHH = 6.5 Hz, 1H, PH), 6.93−7.43 (m, 4H, Ar). 13C NMR
1
(CD2Cl2): δ 12.41 (d, JCP = 29.9 Hz, P-Me), 14.78 (s, CH3CH2O),
64.41 (s, CH3CH2O), 111.54 (d, JCP = 4.4 Hz, CH), 121.02 (d, 1JCP
=
(5) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.;
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Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.;
Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.;
Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao,
O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J.
B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev,
O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.;
Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.;
Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.;
Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman,
J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.;
Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.;
Martin, R. L.; Fox, D. J.; Keith, T.; M. A. Al-Laham, Peng, C. Y.;
Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,
W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision
B.05; Gaussian, Inc., Pittsburgh, PA, 2003.
(6) Ostrowski, A.; Jeske, J.; Jones, P. G.; Streubel, R. J. Chem. Soc.,
Chem. Commun. 1995, 2507. Ali Khan, A.; Wismach, C.; Jones, P. G.;
Streubel, R. Chem. Commun. 2003, 2892.
(7) Marinetti, A.; Mathey, F. Organometallics 1982, 1, 1488.
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45.7 Hz, Ar CP), 121.15 (d, JCP = 9.1 Hz, CH), 131.48 (d, JCP = 6.6
2
Hz, CH), 132.44 (d, JCP = 1.1 Hz, CH), 159.48 (d, JCP = 4.0 Hz,
COCH2), 197.22 (d, 2JCP = 7.2 Hz, cis CO), 200.17 (d, 2JCP = 20.3 Hz,
trans CO). HRMS: m/z 491.9948 (calcd for C14H13O6PW 491.9959).
Synthesis of 3a without Potassium Phosphate. Toluene (3
mL) was added to a mixture of 7-phosphanorbornadiene complex 1a
(200 mg, 0.3 mmol) and phenylboronic acid (187 mg, 1.5 mmol) in a
pressure tube under nitrogen. The tube was sealed and heated to 110
°C for 18 h. The solvent was evaporated, and the residue was strained
onto silica. Purification was performed via cold column chromatog-
raphy (0 °C) with 15/1 hexane/dichloromethane. 3a was obtained as a
white solid (22 mg, 14%).
Reaction of 1a with Trimethyl Borate. Excess B(OMe)3 (1 mL)
was added to a toluene solution (2 mL) of phosphanorbornadiene
complex 1a (200 mg, 0.3 mmol) in a pressure tube under nitrogen.
The mixture was heated with stirring to 110 °C for 20 h. The solvent
was evaporated, and the residue was strained onto silica. Purification
was performed via cold column chromatography (0 °C) with 15/1
hexane/dichloromethane. The yield of the (methoxy)phenylphosphine
complex was 16%. The reaction was repeated in the presence of dry
potassium phosphate (260 mg, 1.2 mmol), and the yield was 20%.
Synthesis of the 1,2,3-Triphenylphosphirene Complex.
Toluene (3 mL) was added to a mixture of 7-phenylphosphanorbor-
nadiene complex 1a (200 mg, 0.3 mmol) and diphenylacetylene (220
mg, 1.2 mmol) in a pressure tube. The tube was sealed and heated to
110 °C for 21 h. The solvent was evaporated, and the residue was
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dx.doi.org/10.1021/om5001138 | Organometallics 2014, 33, 1322−1324