Abstract
4-Nitrophenyl (NP) sulfones have been successfully employed in the modified Julia olefination reaction with carbonyl compounds. The olefination reaction proceeds through a sequence of aldol addition, Smiles rearrangement, and elimination. The sulfones are easily prepared in high yields in a two-step sequence starting from inexpensive commercially available para-fluoronitrobenzenes via nucleophilic aromatic substitution by a mercaptane and subsequent oxidation under standard conditions. The modified Julia reaction between NP sulfones and a wide variety of aromatic aldehydes affords the corresponding styrenes, stilbenes and cinnamate derivatives in yields up to 97% and good stereoselectivities. A mechanistic rationale is advanced to explain the observed results.
Key words
alkene - 4-nitrophenyl sulfone - nucleophilic aromatic substitution - olefination - Smiles rearrangement
References and Notes
1a
Wittig G.
Geissler G.
Liebigs Ann. Chem.
1953,
580:
44
1b
Maryanoff BE.
Reitz AB.
Chem. Rev.
1989,
89:
863
2a
Horner L.
Hoffmann H.
Wippel HG.
Chem. Ber.
1958,
91:
61
2b
Clayden J.
Warren S.
Angew. Chem., Int. Ed. Engl.
1996,
35:
241
3a
Wadsworth WS.
Emmons WD.
J. Am. Chem. Soc.
1961,
83:
1733
3b
Boutagy J.
Thomas R.
Chem. Rev.
1974,
74:
87
4a
Peterson DJ.
J. Org. Chem.
1968,
33:
780
4b
van Staden LF.
Geavestock D.
Ager DJ.
Chem. Soc. Rev.
2002,
31:
195
5
Johnson CR.
Shanklin JR.
Kirchhoff RA.
J. Am. Chem. Soc.
1973,
95:
6462
6
Julia M.
Paris J.-M.
Tetrahedron Lett.
1973,
4833
7a
Baudin JB.
Hareau G.
Julia SA.
Ruel O.
Tetrahedron Lett.
1991,
32:
1175
7b
Baudin JB.
Hareau SA.
Julia SA.
Lorne R.
Ruel O.
Bull. Soc. Chim. Fr.
1993,
130:
856
8 For a recent review about the modified Julia olefination and its application in natural product syntheses, see: Blakemore PR.
J. Chem. Soc., Perkin Trans. 1
2002,
2563
9
Charette AB.
Berthelette C.
St-Martin D.
Tetrahedron Lett.
2001,
42:
5149 ; Corrigendum: Tetrahedron Lett. 2001, 42, 6619
10
Blakemore PR.
Cole WR.
Kocienski PJ.
Morley A.
Synlett
1998,
26
11
Kocienski PJ.
Bell A.
Blakemore PR.
Synlett
2000,
365
For recent examples, see:
12a
Zhu L.
Mootoo DR.
Org. Biomol. Chem.
2005,
3:
2750
12b
Kang J.-S.
Cho EJ.
Ji MK.
Lee YE.
Shin DM.
Choi SY.
Chung YK.
Kim J.-S.
Kim H.-J.
Lee S.-G.
Lah MS.
Lee R.
J. Org. Chem.
2005,
70:
6321
13a
Alonso DA.
Nájera C.
Varea M.
Tetrahedron Lett.
2004,
45:
573
13b
Alonso DA.
Fuensanta M.
Nájera C.
Varea M.
J. Org. Chem.
2005,
70:
6404
14
Truce WE.
Kreider WM.
Brand WW.
Org. React.
1970,
18:
99
15a
Levy AL.
Chung D.
J. Am. Chem. Soc.
1955,
77:
2899
15b
Wieland T.
Mohr H.
Justus Liebigs Ann. Chem.
1956,
599:
222
15c
Khanna IK.
Weier RM.
Yu Y.
Collins PW.
Miyashira JM.
Koboldt CM.
Veenhuizen AW.
Currie JL.
Seibert K.
Isakson PC.
J. Med. Chem.
1997,
40:
1619
16
Pasto DJ.
Cottard F.
Jumelle L.
J. Am. Chem. Soc.
1994,
116:
8978
All synthesized sulfones were employed in analytically pure manner, their data correspond to the literature.
17a Compound 1a: Bost RW.
Turner JO.
Norton RD.
J. Am. Chem. Soc.
1932,
54:
1985
17b Compounds 1b, 1c: Pasto DJ.
Cottard F.
Jumelle L.
J. Am. Chem. Soc.
1994,
116:
8978
17c Compound 1d: Cao S.
Zhang Z.
Fan A.-L.
Huang Z.-M.
Monatsh. Chemie
2003,
134:
529
18
Manchand PS.
Rosenberger M.
Sauci G.
Wehrli PA.
Wong H.
Chambers L.
Ferro MP.
Jackson W.
Helv. Chim. Acta
1976,
59:
387
Analytical data for known olefins correspond to the literature:
19a Compound 2ba: Wenkert E.
Michelotti EL.
Swindell CS.
Tingoli M.
J. Org. Chem.
1984,
49:
4894
19b Compound 2bb: Kudo T.
Nose A.
Yakugaku Zashhi
1975,
95:
1411
19c Compound 2bc: Bernstein PR.
Snyder DW.
Adams EJ.
Krell RD.
Vacek EP.
Willar AK.
J. Med. Chem.
1986,
29:
2477
19d Compound 2bd: Denmark SE.
Sweis RF.
J. Am. Chem. Soc.
2001,
123:
6439
19e Compound 2be: Denmark SE.
Wang Z.
Org. Lett.
2001,
3:
1073
19f Compound 2bf: Bodalia R.
Stern R.
Batich C.
Duran R.
J. Polym. Sci., Part A: Polym. Chem.
1993,
31:
2123
19g Compound 2bg: Denmark SE.
Choi JY.
J. Am. Chem. Soc.
1999,
121:
5821
19h Compound 2bi: Lytollis W.
Scannel RT.
An H.
Murty VS.
Reddy KS.
Barr JR.
Hecht SM.
J. Am. Chem. Soc.
1995,
117:
12683
19i For compound 2ca: analytical data correspond to a commercial sample.
19j Compounds 2cb, 2cg, 2co, 2db: Aggarwal VK.
Fulton JR.
Sheldon CG.
de Vicente J.
J. Am. Chem. Soc.
2003,
125:
6034
19k Compound 2cc: Selvakumar K.
Zapf A.
Spannenberg A.
Beller M.
Chem. Eur. J.
2002,
8:
3901
19l Compounds 2cd, 2ce, 2cf: Dai M.
Liang B.
Wang C.
Chen J.
Yang Z.
Org. Lett.
2004,
6:
221
19m Compounds 2cl, 2dd, 2dg: Masllorens J.
Moreno-Manas M.
Pia-Quintana A.
Roglans A.
Org. Lett.
2003,
5:
1559
19n Compound 2cn: Colberg JC.
Rane A.
Vaquer J.
Soderquist JA.
J. Am. Chem. Soc.
2003,
115:
6065
19o Compounds 2ch, 2ci: Roberts JC.
Pincock JA.
J. Org. Chem.
2004,
69:
4279
19p Compound 2cj: Ali MA.
Kondo K.
Tsuda Y.
Chem. Pharm. Bull.
1992,
40:
1130
19q Compound 2ck: Yasuda M.
Isami T.
Kubo J.
Mizutani M.
Yamashita T.
J. Org. Chem.
1992,
57:
1351
19r Compound 2dc: Costa A.
Nájera C.
Sansano JM.
J. Org. Chem.
2002,
67:
5216
20
Baudin JB.
Hareau G.
Julia SA.
Ruel O.
Bull. Soc. Chim. Fr.
1993,
130:
336
21 Yields and E/Z ratios of the modified Julia olefination with NP sulfones using KHMDS as base after flash chromatography for 2ba: 14% (97:3), 2bb: 55% (>99:1), 2bd: 33% (96:4), 2bg: 58% (95:5), 2ca: 23% (88:12), 2cb: 48% (52:48), 2cd: 32% (94:6), 2cg: 73% (59:41).
22
Blakemore PR.
Ho DKH.
Nap WM.
Org. Biomol. Chem.
2005,
3:
1365
