Allyldiphenylphosphine Oxide1

[4141-48-4]  · C15H15OP  · Allyldiphenylphosphine Oxide  · (MW 242.26)

(reagent for Wittig-Horner reaction;2 substrate for carbon-phosphorus heterocycle3 and 1,3-dipolar cycloaddition4)

Physical Data: mp 108-109 °C;5 1H and 31P NMR studies have been reported.6

Solubility: sol THF; slightly sol ether; insol hexane.

Form Supplied in: white solid; commercially available.7

Preparative Methods: two processes have most commonly been used: (1) rearrangement of allyl diphenylphosphinite2,8,12 and (2) Arbuzov reaction of alkyl diphenylphosphinite with Allyl Bromide.9,13 Other new methods have been also developed.10,14 Structurally related analogs prepared include: 2-methylallyldiphenylphosphine oxide,15 2-phenylallyldiphenylphosphine oxide,15 1-methoxyallyldiphenylphosphine oxide,16 crotyldiphenylphosphine oxide,17 and 1-substituted allylic diphenylphosphine oxide.18

Purification: recrystallization from ether/hexane,2 benzene/petroleum ether,8 cyclohexane,9 or benzene.10

Handling, Storage, and Precautions: thermally stable up to 150 °C.11

Wittig-Horner Reaction.

Lithiated allyldiphenylphosphine oxide condenses with aldehydes in THF-HMPA solution to give (E)-1,3-dienes directly and stereoselectively in good yield2 (for synthesis of 1,3-dienes, see also Allylidenetriphenylphosphorane). This process has been utilized for the synthesis of (E)-trienes (eq 1).19 Condensation with ketones also affords 1,3-dienes (eq 2).2,20

(Z)-Dienes can be prepared with high selectivity by use of a titanium reagent prepared from diphenylphosphinoallyllithium, the metalation product of allyldiphenylphosphine (eqs 3 and 4).2a,2c

The Wittig-Horner reaction of structurally related allylic diphenylphosphine oxides has been widely studied by Warren.18,21 In the absence of HMPA, reaction of lithiated allylic diphenylphosphine oxide with aldehyde affords the Wittig-Horner intermediate alcohol which can be transformed into the 1,3-diene by Sodium Hydride in DMF (eq 5).18a,21a,21b

Geometrically homogeneous crotyldiphenylphosphine oxide can be used to give conjugated diene in which the original (Z) or (E) geometry is retained.17 1-Methoxyallyldiphenylphosphine oxide ylides react at the g-allylic terminus with aldehydes.22

Other Reactions.

Cyclization of allyldiphenylphosphine oxide occurs in the presence of 115% Polyphosphoric Acid (PPA) at 180-200 °C to give carbon-phosphorus heterocycles in modest yield (eq 6).3 Allyldiphenylphosphine oxide undergoes 1,3-dipolar cycloaddition with nitrile oxide to give 3,5-disubstituted D2-isoxazolines (eq 7).4

Related Reagents.

Allylidenetriphenylphosphorane; Allyltributylstannane; Allyltriphenylphosphonium Bromide; Trimethylsilylallyllithium.

1. (a) Maercker, A. OR 1965, 14, 270. (b) Hays, H. R.; Peterson, D. J. Organic Phosphorus Compounds; Kosolapoff, G. M.; Maier, L., Eds.; Wiley-Interscience: New York, 1972; Vol. 3, pp 341-500. (c) Larock, R. C. Comprehensive Organic Transformations; VCH: New York, 1989; pp 173-184. (d) Maryanoff, B. E.; Reitz, A. B. CRV 1989, 89, 863.
2. (a) Ukai, J.; Ikeda, Y.; Ikeda, N.; Yamamoto, H. TL 1983, 24, 4029. (b) Ikeda, Y.; Ukai, J.; Ikeda, N.; Yamamoto, H. T 1987, 43, 723. (c) Burke, S. D.; Armistead, D. M.; Shankaran, K. TL 1986, 27, 6295.
3. El-Deek, M.; Macdonell, G. D.; Venkataramu, S. D.; Berlin, K. D. JOC 1976, 41, 1403.
4. Armstrong, S. K.; Warren, S.; Collington, E. W.; Naylor, A. TL 1991, 32, 4171.
5. Downi, I. M.; Morris, G. JCS 1965, 5771.
6. (a) Gallagher, M. J. AJC 1968, 21, 1197. (b) Clark, P. W.; Curtis, J. L. S.; Garrou, P. E.; Hartwell, G. E. CJC 1974, 52, 1714.
7. Brock, S. L.; Mayer, J. M. IC 1991, 30, 2138.
8. Berlin, K. D.; Calvert, J. F. Proc. Okla. Acad. Sci. 1966, 46, 78.
9. Giguere, R. J.; Herberich, B. SC 1991, 21, 2197.
10. Lu, X.; Zhu, J.; Huang, J.; Tao, X. J. Mol. Catal. 1987, 41, 235.
11. Baechler, R. D.; Blohm, M.; Rocco, K. TL 1988, 29, 5353.
12. (a) Savage, M. P.; Trippett, S. JCS(C) 1966, 1842. (b) Herriot, A. W.; Mislow, K. TL 1968, 3013. (c) Pudovik, A. N.; Aladzheva, I. M.; Spirina, L. V. ZOB 1967, 37, 700. (d) Kormachev, V. V.; Vasil'eva, T. V. ZOB 1988, 58, 770.
13. Collins, D. J.; Mollard, S.-A.; Rose, N.; Swan, J. M. AJC 1974, 27, 2365.
14. (a) Ovsepyan, S. A.; Indzhikyan, M. G. Arm. Khim. Zh. 1985, 38, 377. (b) Antoshin, A. E.; Evreinov, V. I.; Kharitonov, A. V.; Pushin, A. N.; Yarkevich, A. N.; Safronova, Z. V.; Tsvetkov, E. N. IZV 1991, 1860. (c) Rolland, H.; Potin, P.; Majoral, J.-P.; Bertrand, G. TL 1992, 33, 8095.
15. (a) Berlan, J.; Battioni, J.-P.; Koosha, K. TL 1976, 3351. (b) Santelli-Rouvier, C. S 1988, 64.
16. Maleki, M.; Miller, A. TL 1981, 22, 365.
17. Lythgoe, B.; Moran, T. A.; Nambudiry, M. E. N.; Ruston, S.; Tideswell, J.; Wright, P. W. TL 1975, 3863.
18. (a) Davidson, A. H.; Warren, S. JCS(P1) 1976, 639. (b) Davidson, A. H.; Fleming, I.; Grayson, J. I.; Pearce, A.; Snowden, R. L.; Warren, S. JCS(P1) 1977, 550.
19. Ihara, M.; Sudow, I.; Fukumoto, K.; Kametani, T. JOC 1985, 50, 144.
20. Padwa, A.; Krumpe, K. E.; Gareau, Y.; Chiacchio, U. JOC 1991, 56, 2523.
21. (a) Davidson, A. H.; Warren, S. CC 1975, 148. (b) Davidson, A. H.; Warren, S. CC 1976, 181. (c) Davidson, A. H.; Earnshaw, C.; Grayson, J. I.; Warren, S. JCS(P1) 1977, 1452. (d) Grayson, J. I.; Warren, S.; Zaslona, A. T. JCS(P1) 1987, 967.
22. Maleki, M.; Miller, J. A. TL 1981, 22, 3789.

Akira Yanagisawa & Hisashi Yamamoto

Nagoya University, Japan

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