CsOH-promoted P-alkylation: A convenient and highly efficient synthesis of tertiary phosphines

Tetrahedron Letters

Volumn 44, Issue 46, 2003, Pages 8373-8377

  Honaker, Matthew T ^a   Sandefur, Benjamin J ^a   Hargett, James L ^a   McDaniel, Alicia L ^a   Salvatore, Ralph Nicholas ^a  

^a WESTERN KENTUCKY UNIVERSITY   (United States)

Author keywords

Cesium hydroxide; Ditertiary phosphine; Molecular sieves; Secondary phosphine; Tertiary phosphine

Indexed keywords

CESIUM HYDROXIDE; OXIDE; PHOSPHINE DERIVATIVE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; ELECTRON TRANSPORT; MOLECULAR DYNAMICS; OXIDATION; ROOM TEMPERATURE; SYNTHESIS;

EID: 0141894181     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2003.09.117     Document Type: Article

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32. 2 (3×30 mL). The combined organic layers were then washed with degassed basic water (3×30 mL), dried using anhydrous sodium sulfate, decanted, and the solvent was removed in vacuo. Purification via recrystallization from benzene afforded 2 as an air-sensitive white powder (275 mg, 93%).
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34. For reviews on the 'cesium effect', see: (a) Ostrowicki, A.; Vögtle, F. In Topics in Current Chemistry; Weber, E., Vögtle, F., Eds.; Springer-Verlag: Heidelberg, 1992; Vol. 161, p. 37; (b) Galli, C. Org. Prep. Proced. Int. 1992, 24, 287 and references cited therein; (c) Blum, Z. Acta Chem. Scand. 1989, 43, 248.
35. For reviews on the 'cesium effect', see: (a) Ostrowicki, A.; Vögtle, F. In Topics in Current Chemistry; Weber, E., Vögtle, F., Eds.; Springer-Verlag: Heidelberg, 1992; Vol. 161, p. 37; (b) Galli, C. Org. Prep. Proced. Int. 1992, 24, 287 and references cited therein; (c) Blum, Z. Acta Chem. Scand. 1989, 43, 248.
36. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
37. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
38. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
39. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
40. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
41. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
42. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
43. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
44. For cesium base-promoted O-Alkylations, see: (a) Parrish, J. P.; Dueno, E. E.; Kim, S.-I.; Jung, K. W. Synth. Commun. 2000, 30, 2687; (b) Parrish, J. P.; Sundaresan, B.; Jung, K. W. Synth. Commun. 1999, 29, 4423; (c) Chu, F.; Kim, S.-I.; Dueno, E. E.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1847; (d) Kim, S.-I.; Chu, F.; Dueno, E. E.; Jung, K. W. J. Org. Chem. 1999, 64, 4578; (e) Dueno, E. E.; Chu, F.; Kim, S.-I.; Jung, K. W. Tetrahedron Lett. 1999, 40, 1843. For N-Alkylations, see: (f) Salvatore, R. N.; Nagle, A. S.; Jung, K. W. J. Org. Chem. 2002, 67, 674; (g) Salvatore, R. N.; Nagle, A. S.; Schmidt, S. E.; Jung, K. W. Org. Lett. 1999, 1, 1893; (h) Salvatore, R. N.; Shin, S. I.; Nagle, A. S. ; Jung, K. W. J. Org. Chem. 2001, 66, 1035; (i) Salvatore, R. N.; Chu, F.; Nagle, A. S.; Kapxhiu, E. A.; Cross, R. M.; Jung, K. W. Tetrahedron 2002, 58, 3329.
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52. Phosphine 30 was dissolved in deoxygenated benzene and quarternized with benzyl bromide. The solvent and excess BnBr was evaporated in vacuo and the resulting oily residue was triturated with ether, whereupon it immediately crystallized. The optical rotation of the resulting phosphonium salt was compared to the known literature value, see: Horner, L.; Winkler, H.; Rapp, A.; Mentrup, A.; Hoffmann, H.; Beck, P. Tetrahedron Lett. 1961, 161. The optical rotation of the synthetic sample was +37.0° (methanol); reported: 36.8°.
53. 2-elimination was not detected. In this example, 1 was not completely consumed during the reaction, accounting for the additional mass balance.