Allyl Phenyl Sulfone

[16212-05-8]  · C9H10O2S  · Allyl Phenyl Sulfone  · (MW 182.24)

(metalated derivatives serve as ambident nucleophiles; reacts as a 1,1-allylic dianion or 1,1-allylic dipole equivalent1)

Alternate Name: 1-phenylsulfonyl-2-propene.

Physical Data: bp 111-113 °C/0.5 mmHg; d 1.189 g cm-3.

Solubility: insol water; sol most organic solvents.

Form Supplied in: colorless liquid with purity >98% as obtained commercially.

Preparative Method: from Allyl Bromide and benzenesulfinate in ethanol according to the original procedure2 is most straightforward and avoids the use of strong-smelling thiols.

Purification: distillation in vacuo prior to use.

Handling, Storage, and Precautions: the sulfone is a stable compound and is handled without special precaution.

Metalation.

Treatment with n-Butyllithium in THF produces lithiated allyl phenyl sulfone. Structurally, the lithiated reagent is akin to a lithium dienolate in that it possesses an O-Li contact, and a C-1-S bond which has double bond character, although the X-ray structure of the diglyme solvate indicates that C-1 does not possess full sp2 character.3 In THF, the reagent alkylates through C-a in a manner similar to the sulfide and sulfoxide.1 Carbonyl addition also proceeds in this mode.4 However, with Michael acceptors, the behavior is intermediate between that of the sulfide and sulfoxide: acyclic unsaturated ketones and unsaturated esters undergo predominantly conjugate (or 1,4-) addition through C-a while cyclic enones preferentially undergo conjugate addition through C-g.5,6 The addition proceeds under kinetic control with high diastereoselectivity and is analogous to the sulfoxide reaction (see Allyl Phenyl Sulfoxide).6c However, Hexamethylphosphoric Triamide causes conjugate addition to both acyclic and cyclic enones through C-a to occur, the latter reaction paralleling that of the lithiated sulfide (see Allyl Phenyl Sulfide).6 Lithiated allyl phenyl sulfone adds through C-a to a bisepoxide to give a single adduct which, after internal proton transfer, undergoes cyclization to a precursor of brefeldin A (eq 1).7

Sulfonyl Leaving Group.

Allylic phenyl sulfones undergo regio- and stereoselective allylic displacement by lithium dialkylcuprates8 and sodium diethyl malonate in the presence of Pd0 catalysts9 in good yields. Like the sulfides, the sulfones undergo radical fragmentation.10 Addition of tributyltin radical followed by loss of the arylsulfonyl radical affords the allylically transposed stannane. Acid hydrolysis then gives the terminal alkene without contamination with the other regioisomer.10a,10b The reaction is not applicable to g-alkylallylic sulfones. The stannane reacts with sym-trioxane in the presence of a Lewis acid catalyst with concomitant destannylation, thereby rendering the allylic sulfone functionally equivalent to a 1,1-dianion (eq 2).10b Alkenes are prepared by a-alkylation of lithiated allyl phenyl sulfone followed by conversion into the vinyl sulfone with Potassium t-Butoxide in THF,11,12 and then reductive cleavage of the phenylsulfonyl group with lithium in ethylamine.11 a-Alkylation of lithiated allylic phenyl sulfones bearing other alkyl or functional groups followed by base-induced elimination13 or reductive cleavage14 is used in the synthesis of polyenes such as vitamin A and squalene. The weak Lewis basicity of the sulfonyl group enables allylic phenyl sulfones to be activated by Lewis acids in Friedel-Crafts alkylation of aromatic rings with displacement of the phenylsulfonyl group.15 Thus alkylation of lithiated allyl phenyl sulfone followed by the Friedel-Crafts reaction renders the sulfone functionally equivalent to a 1,1-dipole. A conjugate addition-enolate trapping sequence commencing with DMPU-induced conjugate addition of lithiated prenyl tolyl sulfoxide to 2-methylcyclopentenone provides an adduct which undergoes Lewis acid-catalyzed intramolecular cyclization to a 1,11-epithio steroid (eq 3).15b The dipolar characteristic of allylic sulfones is also illustrated in the synthesis of chrysanthemic acid from lithiated prenyl phenyl sulfone.16 The conjugate adduct with dimethylacrylate undergoes an internal nucleophilic displacement of the phenylsulfonyl group to form the cyclopropane (eq 4). A preparation of prephytoene is carried out in similar fashion.17 Lithiated allyl phenyl sulfone couples with iodocarbenoids to form 1-iodo-1,3-dienes in high yields and with high stereoselectivity for the E-isomer.18

Related Reagents.

Allyl Phenyl Sulfide; Allyl Phenyl Sulfoxide; a-Phenylsulfonylethyllithium.


1. (a) Magnus, P. D. T 1977, 33, 2019. (b) Block, E. Reactions of Organosulfur Compounds; Academic Press: New York, 1978. (c) Biellmann, J.-F.; Ducep, J.-B. OR 1982, 27, 1.
2. Otto, R. LA 1894, 283, 18; Cope, A. C.; Morrison, D. E.; Field, L. JACS 1950, 72, 59. Vennstra, G. E.; Zwaneburg, B. S 1975, 519.
3. Gais, H.-J.; Vollhardt, J.; Lindner, H. J. AG(E) 1986, 939. Boche, G. AG(E) 1989, 277 and references cited.
4. Cuvigny, T.; Herve du Penhoat, C.; Julia, M. T 1986, 42, 5329.
5. Kraus, G. A.; Frazier, K. SC 1978, 8, 483.
6. (a) Hirama, M. TL 1981, 22, 1905. (b) Vasil'eva, L. L.; Mel'nikova, V. I.; Gainullina, É. T.; Pivnitskii, K. K. JOU 1983, 19, 835. (c) Binns, M. R.; Haynes, R. K.; Katsifis, A. G.; Schober, P. A.; Vonwiller, S. C. JOC 1989, 54, 1960.
7. Miyaoka, H.; Kajiwara, M. CPB 1985, 33, 2531.
8. Masaki, Y.; Sakuma, K.; Kaji, K. CC 1980, 434.
9. Trost, B. M.; Schmuff, N. R.; Miller, M. J. JACS 1980, 102, 5979.
10. (a) Ueno, Y.; Aoki, S.; Okawara, M. JACS 1979, 101, 5414. (b) Ueno, Y.; Aoki, S.; Okawara, M. CC 1980, 683. (c) Giese, B.; Erdmann, P.; Göbel, T.; Springer, R. TL 1992, 33, 4545.
11. Savoia, D.; Trombini, C.; Umani-Ronchi, A. JCS(P1) 1977, 123.
12. Sataty, I.; Meyers, C. Y. TL 1974, 4161.
13. Julia, M.; Arnould, D. BSF(2) 1973, 746. Manchand, P. S.; Rosenberger, M.; Saucy, G.; Wehrli, P. A.; Wong, H.; Chambers, L.; Ferro, M. P.; Jackson, W. HCA 1976, 59, 387. Fischli, A.; Mayer, H.; Simon, W.; Stoller, H.-J. HCA 1976, 59, 397.
14. Grieco, P. A.; Masaki, Y. JOC 1974, 39, 2135. Olson, G. L.; Cheung, H.-C.; Morgan, K. D.; Neukom, C.; Saucy, G. JOC 1976, 41, 3287.
15. (a) Trost, B. M.; Ghadiri, M. R. JACS 1984, 106, 7260. (b) Adams, J. P.; Bowler, J.; Collins, M. A.; Jones, D. N.; Swallow, S. TL 1990, 31, 4355.
16. Martel, J.; Huynh, C. BSF(2) 1967, 985. Schatz, P. F. J. Chem. Educ. 1978, 55, 468.
17. Campbell, R. V. M.; Crombie, L.; Findley, D. A. R.; King, R. W.; Pattenden, G.; Whiting, D. A. JCS(P1) 1975, 897.
18. Charreau, P.; Julia, M.; Verpeaux, J. N. BSF(2) 1990, 275.

Richard K. Haynes

Hong Kong University of Science and Technology, Kowloon, Hong Kong

Simone C. Vonwiller

The University of Sydney, NSW, Australia



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