5377
J. Org. Chem. 1993,58, 5377-5385
[2,3]-Sigmatropic Rearrangement of @-PhenylsulfonylPropargylic Sulfenates as a Method for Preparing 1,4-Bis(phenylsulfonyl)-1,3-butadienes Xiaoheng Wang,t Zhijie Ni,t Xiujing Lu,t Andrea Hollis,? Harold Banks,$ August0 Rodriguez,'J and Albert Padwa'd Department of Chemistry, Clark Atlanta University, Atlanta, Georgia 30314, Department of Chemistry, Emory University, Atlanta, Georgia 30322, and U. S. Army, Chemical Research Development and Engineering Center, Aberdeen Proving Ground, Maryland 21010 Received May 5, 19930
Several8-sulfoxy-substituted acetylenic carbinols were prepared by the addition of thiyl radicals and oxygen to conjugated enynes. The products obtained are derived from thiyl radical attack at the olefinicbond to generate a propargylic radical. Capture of this radical by oxygen followed by hydrogen transfer from thiophenol gives a hydroperoxide intermediate, which undergoes oxygen transfer by both intra- and intermolecular pathways. The resultant 8-phenylsulfiiyl propargylic alcohols proved to be versatile intermediates for the preparation of several different classes of compounds. The [2,31-sigmatropic sulfinate to sulfoxide rearrangement was found to give 1,4-bis(phenylsulfonyl)l,&butadienes, &-unsaturated phenylsulfoxy ketones, and 8-phenylsulfonyl a-allenic sulfoxides. Oxidation of the sulfoxy moiety to the sulfone followed by sulfinate formation with phenylsulfenyl chloride produces, after [2,31-sigmatropicrearrangement, B-phenylsulfonyl a-allenic sulfoxides. In certain cases these allenes could be isolated, but were usually isomerized in situ and further oxidized to give 1,4-bis(phenylsulfonyl)-l,3-butadienes.The [2,3]-sigmatropic rearrangement of &phenylsulfinyl-substituted propargylic alcohols proceeds by an entirely different course. With these systems, a double sigmatropic process occurs leading to the formation of vinyl sulfinates which are readily hydrolyzed to give ar,&unsaturated phenylsulfoxy ketones. Conjugated dienes with electron-donating or electronwithdrawing substituents have attracted considerable attention during recent years.14 Sulfur-substituted dienes, in particular, have been widely used in the Diels-Alder readion? More recently, phenylsulfonyl-substituteddienes have become established as useful synthetic interm e d i a t e ~ . ~The ' ~ phenylsulfonylgroup not only increases the reactivity of the diene but also adds control to the 7 Clark Atlanta University. t Emory University.
8 Edgewood Research,Development and Engineering Center.
Abstract published in Advance ACS Abstracts, August 15, 1993. (l)Daniehefsky, S. Acc. Chem. Res. 1981, 14, 400. Grayeon, 3.4.; Petrizilka, M. Synthesis 1981,753. Hickmott, P. W. Tetrahedron 1984, 40,2989. (2) Evans, D. A.; Bryan, C. A.; Sims, C. L. J. Am. Chem. SOC.1972,94, 2891. Troet, B. M.; Vladuchick, W. C.; Bridges, A. J. J. Am. Chem. SOC. 1980,102,3554. Cohen, T.;Kosaych, Z. J. Org. Chem. 1982,47,4005. (3) Halazy, S.;Magnue, P. TetrahedronLett. 1984,25,1421. Posner, G. H.; Wettlaufer, D. G.J. Am. Chem. SOC.1986,108,7373. Poener, G. H.; Harrison, W. J . Chem. SOC.,Chem. Commun. 1985,1786. (4) Akemark, B.; NyetrBm, J. E.; Rein, T.;BAcckvall, J. E.; Helquist, P.; Aslanian, R. TetrahedronLett. 1984,25,5719. Bloom, A. J.; Mellor, J. M. Tetrahedron Lett. 1986,27,873. (5) Organic Chemistry of Sulfur; Oae, S., Ed.;Plenum: New York, 1977. Bernardi, F.; Mangini, E. Organic Sulfur Chemistry: Theoretical and Experimental Adoances; Elsevier: Amsterdam, 1985. (6) Padwa, A.; Murphree, 5.S. Org. Prep. Proced. Znt. 1991,23,545. (7) 'host, B. M. Bull. Chem. SOC.Jpn. 1988,61,107. (8)Magnue, P. D. Tetrahedron 1977,33,2019. (9) Schank, K. Methoden der Organkchen Chemie (Houben-Weyl), 4th ed.;Thieme; Stuttgart, 1986; Vol. E l l , p 1129. (10) Durst, T.Comprehensiue Organic Chemistry;Barton,D. H. R.; O h ,W. D., Eda.; Pergamon Press: Oxford, 1979; Vol. 3, pp 171, 197. (11) The Chemistry of Sulfones and Sulfoxides;Patai, S., Rappaport, Z., Stirling, C. J. M., Me.; Wiley Chichester, l98& pp 1-1210. (12) Fuchs, P. L.; Braish, T.F. Chem. Reo. 1986,86,903. (13) Julia, M.; Paris, J. M. TetrahedronLett. 1973,12,4833. Hird, N. W.; Lee, T.V.; Leigh, A. J.; Maxwell, J. R.; Peakman, T.M. Tetrahedron Lett. 1989,30,4867. Kociemki,P. Phosphorus Sulfur Relat. Elem. 1985, 24,97-127. (14) Lythgoe, B.;Waterhouse, I. J . Chem. Soc., Perkin Trans. 1 1979, 2429.
regioselectivity of the cycloaddition. Indeed, the phenylsulfonyl moiety is enjoying increasing popularity as an activating group undoubtedly as a consequenceof ita ability to act as a temporary control element in organic synthesis. The sulfonyl group can be removed both reductively and oxidatively with subsequent formation of ketones.lS It stabilizes adjacent carbanions1swhich are extremely useful in carbon-carbon bond forming reactions. Benzenesulfnate anion also serves as a leaving group with SN1-reactive s u b s t r a t e ~ and ~ ~ Jin ~ the formation of ~yclopropanes.~9 Elimination to olefins can also be accomplished, as for example, in the second step of the Julia alkene synthesis.20 The bulky1 phenylsulfonyl group has also been shown to be useful for acyclic stereocontrolm21 In earlier reports, we demonstrated the use of 1,3- and 2,3-bis(phenylsulfonyl)-l,3-butadienesas versatile building blocks in organic synthesis, particularly for [4
+
~~
(15) Little,R.D.;Myong,S. 0.TetrahedronLett.1980,21,3339. H m , J. R. J. Org. Chem. 1983,48,4432. Tanaka,K.; Mataui, S.;Kaji, A. Bull. Chem. SOC.Jpn. 1980,53, 3619. (16)Trost, B. M. Angew. Chem., Znt. Ed. Engl. 1989, 28, 1173. Biellmann, J. F.; Ducep, J. B. Org. React. 1982,27, 1. (17) Brown, D. S.;Ley, S. V. TetrahedronLett. 1988,29,4869. Brown, D. S.; Hanason, T.;Ley, S. V. Synlett 1990,48. Hamata, S.; Gamlath, C. B. J. Org. Chem. 1988,53,6156. Trost, B. M.; Mikhail, G. K. J . Am. Chem. SOC.1987,109,4124. (18) Hoffmann, H. M. R. J . Chem. SOC.1965,6762. (19) Martel, J.; Huynh, Ch. Bull. SOC.Chim. Fr. 1967,985. Julia, M.; Guy-Ronalt, A. Bull. SOC.Chim.Fr. 1967,1411. Parker,W.L.;Woodward, R. B. J. Org. Chem. 1969,34, 3085. Campbell, R. V. M.; Crombie, L.; Findley, D. A. R.; Kw,R. W.; Pattenden, G.; Whiting, D. A. J. Chem. SOC.,Perkin Trans. 1 1975, 897. (20) Alvarez, E.; Cuvigny, T.;Hervee, J., du Penhoat, C.; Julia, M. Tetrahedrron 1988,44,119. Fehr, C . Helo. Chim. Acta 1983,66,2519. Mitchell,R.H.;Yan,J.-S.H.;Dingle,T.-W. J.Am. Chem.Soc. 1982,104, 2551. Mandai,T.; Yanagi, T.; Araki,K.;Morisaki,Y.; Kawada, M.;Otera, J. J . Am. Chem. SOC.1984,106,3670. (21) Najera, C.; Mancheno, B.; Yue, M. Tetrahedron Lett. 1989,30, 6085.
0022-3263/93/1958-5377$04.00/00 1993 American Chemical Society
6378
J. Org. Chem., Vol. 58, No. 20,1993
21-cycloaddition c h e m i ~ t r y . As ~ ~part * ~ ~of our studies in this area, we set out to prepare several l,4-bis(pheny1sulfonyl) 1,3-dieneswith the intention of comparing their reactivity and cycloaddition behavior with the correAlthough there are quite sponding 1,3-and 2,3-i~omers.~~ a number of synthetic routes available for the synthesis of monosulfonated dienes,2C30methods for preparing bis(phenylsulfonyl)-substituteddiene@ are quite limited and not easily amenable to the preparation of the 1,4-isomer. In a preliminary report, we demonstrated that sulfinic esters of 0-phenylsulfonyl-substituted acetylenic carbinols undergo a smooth reorganization to allenic sulfoxides, which, in turn, can be isomerized with base and oxidized to afford 1,4-bis(phenylsulfonyl)1,3-diene~.~~ Our ongoing interest in the generality and synthetic utility of the [2,31sigmatropic rearrangement method33inspired us to take a detailed look at the scope and mechanistic details of this process. The present paper documentsthe results of these studies.
Wang et al. sulfoxides37 and employs excess base to isomerize allene 2 to diene 3. The first system we chose to examine was
q oxid. H
1
carbinol 5. This compound was prepared in 88% overall yield by addition of the lithio anion of methyl phenyl sulfoxide to 3-(trimethylsilyl)-2-propynalfollowed by desilylation and oxidation (Oxone). Treatment of 6 with 1 equiO of benzenesulfenyl chloride and 2 equiv of triethylamine in CHzClz at 0 "C afforded allene 6 which was rapidly converted to diene 7 (n = 1) in 62% yield.
0
n
t ii PhSCH2Li + HCC=CSiMe3 Results and Discussion the reversible Since its discovery two decades interconversion of allylic sulfenates to sulfoxides has become one of the most studied and synthetically useful [2,3]-sigmatropic remangementa known. Numerous synthetic applications of the rearrangement have been reported, including ita use in the total synthesis of a variety of natural products such as steroids, prostaglandins, and le~kotrienes.3~ Our strategy for the synthesis of 1,4-bis(phenylsulfonyl)-l,&dienes relies on the well-precedented [2,3]-sigmatropicshift of propargylicsulfenates to a-allenic (22) Padwa, A.; Norman, B. H. Tetrahedron Lett. 1988, 29, 2417. Norman, B. H.; Gareau, Y.; Padwa, A. J. Org. Chem. 1991,56, 2154. Padwa, A,; Harrison, B.; Norman, B. H. TetrahedronLett. 1989,30,3259. Padwa, A.; Gereau, Y.; Harrison, B.; Norman, B. H. J. Org. Chem. 1991, 56,2713. Padwa, A.; Gareau,Y.; Harrison, B.; Rodriguez,A. J. Org.Chem. 1992,57, 3540. (23) For cycloadditionchemistry of phenylsulfonyl-substituted dienes, see: BHckvall, J. E.; Rise, F. TetrahedronLett. 1989,30,5347. BAckvall, J. E.; Juntunen, S. K. J. Am. Chem. SOC.1987,109,6396. Chou, T.-S.; Hung, S. C. J. Org. Chem. 1988,53,3020. Chou, TA.; Hung, S. C.; Tso, H. H. J. Org. Chem. 1987,52,3394. Bickvall, J. E.; Juntunen, S. K. J. Org. Chem. 1988,53, 2398. Mashyama, Y.; Yamazaki,'H.; Toyoda, Y.; Kurusu, Y. Synthesis 1986,964. Lee, S. J.;Lee, J.-C.; Peng, M. L.; Chou, T.-S. J. Chem. SOC.,Chem. Commun. 1989,1020. Overman, L. E.; Petty, C. B.; Ban, T.; Huang, G. T. J. Am. Chem. SOC.1983,105,6335. Eisch, J. J.; Galle, J. E.; Hallenbeck, L. E. J. Org. Chem. 1982,47, 1608. (24) Andell, 0. S.; BHckvall, J. E. Tetrahedron Lett. 1986,26, 4555. (25) Cuvigny,T.; Hervee du Penhoat, C.; Julia, M. Tetrahedron 1988, 42,5329. Tetrahedron Lett. 1983,4315. (26) Inomata, K.; Kinoehita, H.; Takemoto, H.; Murata, Y. Bull. Chem. SOC.Jpn. 1978,51, 3341. (27) Chou, T.; Lee, S. J.; Peng, M. L.; Sun, D. J.; Chou, S. S.P. J. Org. Chem. 1988,53, 3027. (28) Naf, F.; Decorzant, R.; Escher, S. D. Tetrahedron Lett. 1982,23, 5043.
(29)Akermark,B.;Myatrom,J.E.;Rein,T.;BHckvd, J.E. Tetrahedron Lett. 1984,25, 5719. (30) Marino, J. P.; Long, J. K. J. Am. Chem. SOC.1988, 110, 7916. (31) Jeganathan,S.;Okamura, W. H. TetrahedronLett.1982,23,4763. Maeuyama, Y.; Sato, H.; Kurueu, Y. Tetrahedron Lett. 1986,26, 67. (32) Ni, 2.;Wang, X.;Rodriguez, A,; Padwa, A. Tetrahedron Lett.
1992,33,7303. (33) Padwa, A.;Bullock, W. H.; Norman, B. H.; Perumattam, J. J. Org. Chem. 1991,56,4252. (34) Miller, E. G.; Rayner, D. R.; Mislow, K. J. Am. Chem. SOC.1966, 88, 3139. Mislow, K. Rec. Chem. h o g . 1967, 28, 217. Evans, D. A,; Andrew, G. C. Acc. Chem. Res. 1974, 7,147. (35) Braverman, S.; Stabinsky, Y. J. Chem. Soc., Chem. Commun. 1967, 270. (36) Braverman, S. In The Chemistry of Sulfones and Sulfoxides;
Patai, S., Rappoport, Z., Stirling, C. J., E&.; John Wiley: New York, 1988.
3
2
-
0
f
PhSCH2CHC=CSiMe3
I
OH
1) K2ml
2) Oxon&
4
9SPh
6
HwSOnPh
7;n=l 8n=2
Oxidation of sulfoxide 7 with Oxone in methanol-water gave 1,4-bis(phenylsulfonyl)-l,3-butadiene8 (n = 2) in 97% yield. As part of our general program in this area, we decided to prepare a series of related 1,4-bis(phenylsulfonyl) 1,3dienes so as to evaluate their chemical reactivity. In order to accomplish this goal, we required an efficient method to synthesize a variety of 0-sulfur-substitutedynols. While several useful syntheses of acetylenic carbinols have been a simple and general method for the preparation of 0-sulfoxy-substituted p o l s has not been established. To overcome this problem, we developed ageneral synthesis of these substrates through the coaddition of thiyl radicals and oxygen to olefins, a process termed c o o ~ i d a t i o n . 3Our ~ ~ ~synthetic plan was based on the assumption that thiyl radical attack would occur a t the ~~
~
~
~~
(37) Theobald, P. G.; Okamura, W. H. J. Org. Chem. 1990,55, 741. Cutting, I.; Parsom, P. J. J. Chem. SOC.,Chem. Commun. 1983, 1209. (38) Chanley, J. D. J. Am. Chem. SOC. 1948, 70,244. Marshall, J. A.; Wang, X. J. Org. Chem. 1991, 56, 4913. Mandai, T.; Nakata, T.;
Murayama, H.; Yamaoki, H.; Ogawa, M.; Kawada, M.; Tsuji, J. Tetrahedron Lett. 1990,31, 7179. Earl, R. A.; Towneend, L. B. Org. Synth. 1981,60,81. Theobald, P. G.; Okamura, W. H. J.Org. Chem. 1990,55,
741. (39) Wang, X.;Ni, 2.;Lu, X.;Smith, T. Y.; Rodriguez, A.; Padwa, A. Tetrahedron Lett. 1992,34,5917. (40) Kharasch, M. S.; Nudenberg, W.; Mantell, G. J. J. Org. Chem. 1961,16,524. Oswald,A. A.; Griesbaum,K.; Hudson, B. E., Jr.; Bregman, J. M. J. Am. Chem. SOC.1964,86,2877. Griesbaum, K.; Oswald, A. A.; Hudson, B. E., Jr. J. Am. Chem. SOC.1963,85,1969. (41) Petrov, A. A.; Sulimov, G. J. Org. Chem. USSR (Engl. Troml.) 1966,2,770. Stadnichuk, M. D.; Kryukova, T. B.; Petrov, A. A. J. Gen. Chem. USSR (Engl. "ranel.) 1976,45,803. The addition of thiyl radicals
to conjugated enynes with an alkoxy or thioalkoxy substituent on the double bond occurs exclusively at the terminal alkyne position: Shoetakovskii, M. F.; Bogdanova,A. V.; Plotnikova, G. I.; Andreve, N. s.Bull. Acad. Sci. USSR,Diu. Chem.Sci. (Engl. Tranal.) 1960,1185. Prilezhaeva, E. N.; Guseinov, I. I.; Lopatin, B. V.; Shostakovskii, M. F. J.Gen. Chem. USSR (Engl. Transl.) 1969,2, 770.
J. Org. Chem., Vol. 58, No.20, 1993 5379
Preparation of 1,4-Bis(phenylaulfonyl)-1,3-butadienes
Table I. Cooxidation of Conjugated Enynes conditions
enyne
produde
12
diaeter ratio 1.5:l
13 = 33% 14 = 10%
1:l
16 = 21% 17 = 13%
1.2:1
19 5 49% 20 512%
14
13
p?c:q 0
RSH
__c
9
H&
SIMe
25%
15
F%
PhSl:
48 h) or KBr is added as acoreagent (vide infra), the amount of sulfoxy carbinol is enhanced. &Thiophenyl carbinols are the exclusive products if a stoichiometric amount of triphenylphosphine is added to the reaction mixture. Conjugated enynes possessing an internal acetylene gave higher yields of product and proved less problematic than enynes with terminal acetylenes. The cooxidation of enynes proved to be highly regioselective. In all of the cases examined, the products formed are derived by preferential attack of the thiyl radical on the double bond of the enyne. The regiochemistry encoun-
24
25
tered holds for conjugated enynes that contain internal as well as terminal acetylenic *-bonds. These results are consistent with earlier observations on the addition of thiyl radicals to conjugated enynes41but are in marked contrast to recent studies by Back and c o - ~ o r k e r s .The ~ ~ Back group investigated the free radical selenosulfonation of several conjugated enynes and found that the regioselectivity of the addition is controlled by steric factors. When the enyne contains an internal alkyne, radical addition occurs at the doublebond. However, addition to the triple bond occurred preferentially with enynes possessing a terminal acetylenic ?r-bond. These differences are not all that surprising,however, since radical addition to conjugate enynes are complex and the regiochemistry is not only substrate-dependent but also depends on the nature of the attacking radical species.a In contrast to the acyclic enynes, the cooxidation of cyclic enyne 26 gave sulfoxy carbinol 27 (26 ?6) as a single diastereomer as well as a lesser amount (14%) of sulfide 28. The structure of 27 has both the sulfoxy and hydroxyl groups in the equatorial position (trans),this assignment being based on an axial coupling constant of J = 12.9 Hz for the C2-hydrogen. The fact that out of four possible diastereomers only one is observed is worth noting and suggests an intramolecular oxygen atom transfer process (vide infra). Sulfide 28 was convertedto a mixture of EIZ aldehydes 29 using aqueous methanol containing a trace of silver carbonate (Rupe rearrangementu). When the silyl-protected enyne 30 was cooxidized, sulfoxide 31 and sulfide 32 were formed in a 3:2 ratio. Once again, sulfoxy carbinol 31 was obtained as a single diastereomer even though four are possible. Desilylation of 31 with fluoride ion gave sulfoxide 27, the same product obtained from the cooxidation of enyne 26. When sulfide (42) Back, T. G.; Lai, E. K.Y.;Muralidharan, K. R. J. Org. Chem. 1990,55,4595. (43) Poutema, M. L.;Ibarbia, P. A. J. Am. Chem. SOC. 1973,95,6000. Poutema, M. L.; Ibarbia, P. A. J. Org. Chem. 1971,362572. Poubma, M. L.;Ibarbia, P. A. J. Org.Chem. 1970,36,4038. Petry, R. C.; Parker, C. 0.;Johnaon, F.A.; Stevens, T. E.; Freeman, J. P. J. Org.Chem. 1967, 32, 1534. (44) Pelletier, S. W.; Mody, N.V. J. Org. Chem. 1976,41,1069.
5380 J. Org. Chem., Vol. 58, No. 20, 1993
Waug et al. Scheme I
-
R1 PhS'
+
H2C\
R2
R2
26
PhSCHb
