Regiochemical and Stereochemical Studies on Halogen-Induced Ring Expansions of Unsaturated Episulfides

Journal of Organic Chemistry

Volumn 60, Issue 20, 1995, Pages 6484-6495

  Ren, Xiao Feng ^a   Konaklieva, Monika I ^a   Turos, Edward ^a   Krajkowski, Lynn M ^a   Lake, Charles H ^a   Janik, Thomas S ^a   Churchill, Melvyn Rowen ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001333953     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00125a039     Document Type: Article

References (107)

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81. In a formal sense, these ring-expansions are related to those of unsaturated epoxides reported by: Padron; J. I.; Vasquez, J. T.; Morales, E. Q.; Zarraga, M.; Martin, J. D. Tetrahedron: Asymmetry 1992,3, 415.
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89. There does appear to be precedent for 5-endo-trig cyclizations of sulfenyl halides that lack the a-hydroxy substituent. Lautenschlae- ger reported that the reaction of 1,4-pentadiene with SCI2 gives a 65: 35 mixture of five- and six-membered ring products in 39% yield (ref 9). To account for the formation of the five- membered ring adduct, the author postulates a 5-endo-trig sulfenyl chloride ring closure from sulfenyl chloride ii as a major pathway leading to this product. In his discussion, Lautenschlaeger points out that this route would most likely require the formation of a secondary carbocation iii (rather than an episulfonium ion), which to us seems unlikely and unnecessary since the formation of both v and vi can occur by ring closure of the isomeric sulfenyl halide ii through episulfonium intermediate iv. Also, Vedejs has executed an acid-promoted 5-endo-trig ring closure of a sulfenyl acetate onto a conjugated diene, in which the high stereochemical control observed in the reaction is strongly suggestive of an episulfonium intermediate, Vedejs, E.; Buchanan, R. A.; Conrad, P. C.; Meier, G. P.; Mullins, M. J.; Schaffhausen, J. G.; Schwartz, C. E. J. Am. Chem. Soc. 1989, 111, 8421.
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91. Episulfonium ions have been postulated as intermediates in the reaction of sulfenyl halides with olefins to account for the trans stereochemistry and preference for forming anti-Markovnikoff adducts. For studies and discussions, see: Kartashov, V. R.; Skorobogatova, E. V.; Grudzinskaja, E. Yu.; Akimkina, N. F.; Zefirov, N. S.; Caple, R. Tetrahedron 1985, 41, 5219.
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97. Conversely, the a- and β-vinyl protons of endocyclic vinyl sulfones usually give overlapping signals. For an example, see: Becker, K. B.; Labhart, M. P. Helv. Chim. Acta 1983, 66, 1090.
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100. Sulfenyl halide cyclizations have been utilized in the synthesis of bicyclic β-lactams wherein the presence of the four-membered lactam ring promotes the 5-exo-trig ring closure. Thus, bromination of disulfide vii reportedly gives five-membered ring product ix in quantitative yield as the kinetic product of the reaction. Upon standing at room temperature in solution, ix isomerizes cleanly to the six-membered ring x through the episulfonium ion viii (eq i) (Kamiya, T.; Teraji, T.; Saito, Y.; Hashimoto, M.; Nakaguchi, O.; Oku, T. Tetrahedron Lett. 1973, 14, 3001).
101. A closely related procedure was reported for the acid- catalyzed isomerization of azetidinyl disulfides such as xi. In this instance, protonation leads to the generation of an episulfonium species xii which undergoes nucleophilic ring opening to afford only adduct xiii, the product of 5-exo-trig cyclization (eq ii) (Alpegiani, M.; Giudici, F.; Perrone, E.; Borghi, D. Tetrahedron Lett. 1990, 31, 3509).
102. These isomerizations closely resemble the classical Morin rearrangement of penicillin sulfoxides, an isomerization that is mediated by the formation and cyclization of an electrophilic sulfur species onto a double bond. (Morin, R. B.; Jackson, B. G.; Mueller, R. A.; Lavagnino, E. R.; Scanlon, W. B.; Andrews, S. L. J. Am. Chem. Soc. 1963, 85, 1896.)
103. For discussions and references, see: Cooper, R. D. G.; Hatfield, L. D.; Spry, D. O. Acc. Chem. Res. 1973, 6, 32.
104. Chemistry and Biology of ji-Lactam Antibiotics, Morin, R. B., Gorman, M., Eds.; Academic Press: New York, 1982; Vol. 1.
105. For related reactions involving an intramolecular sulfenylation of an allenyl azetidinone system, see: Farina, V.; Kant, J. Tetrahedron Lett. 1992, 33, 3559.
106. An alternative mechanism which can be envisioned for the cyclization of xiv is a stepwise addition of sulfenyl halide to the olefin to give a tetravalent sulfur intermediate xv, which could provide episulfonium ion xvi in a separate mechanistic step (eq iii). Support for this pathway can be found from early NMR studies on the reverse process, the halide-promoted desulfurization of methylepisulfonium ion xvii, which is thought to occur via nucleophilic attack by chloride on the electropositive sulfur center to give tetravalent sulfur species xviii (Owsley, D. C.; Helmkamp, G. K.; Rettig, M. F. J. Am. Chem. Soc. 1969, 91, 5239). This species is postulated to spontaneously destruct to either olefin xix or the trans-β -chloro sulfenyl chloride adduct xx (eq iv). Evidence for the formation of tetravalent sulfur species xviii is from the shift in the 'H NMR signal for the episulfonium methyl group at low temperature upon addition of chloride ion. While we agree that species xviii could be expected to form rapidly under the reaction conditions, it may not necessarily be responsible for the formation of the observed products. Otherwise, microscopic reversibility would dictate that the addition of the sulfenyl chloride to the olefin must necessarily proceed through this tetravalent species. We favor the concerted mechanism for formation of the episulfonium intermediate, which would appear to benefit from a lower transition state energy than the valency-expanded sulfur species (which requires energy to rehybridize).
107. Mouzin, G.; Cousse, H.; Rieu J.-P.; Duflos, A. Synthesis 1983, 117.