The Nitro group in organic sysnthesis - Feuer

5.7 INTRODUCTION OF HETEROATOMS TO NITROALKANES 149

The reaction of 1-nitrocyclohexene with triphenylbismuth dichloride in the presence of triethylamine gives the deconjugated arylated product, as shown in Eq. 5.69.108

Aryllead triacetates are also good reagents for arylation of stabilized carbanions, including the anion of nitroalkanes (Eq. 5.70).109 As a related reaction, α-vinylation110 or α-acetylation111 of nitro compounds is possible using vinyllead triacetates or alkynyllead triacetates.

(5.70)

DMSO

76%

In recent years, a variety of hypervalent iodine reagents have been available. The versatility of these hypervalent organoiodine reagents in organic synthesis has been well recognized. Diaryliodonium salts constitute an important reagent class for the transfer of aryl groups. These iodonium ion salts have been used effectively in C-arylation of a variety of nucleopohiles.112

The arylation of the anion of nitroalkanes with diaryliodonium salts was already reported in 1963.113

Intramolecular cyclization using palladium-catalyzed arylation of nitro compounds has been reported recently (Eq. 5.71).114

NO2 NO2

PdCl2(PPh3)2

(5.71)

Cs2CO3

O O

O O

Br

58%

Buchwald and co-workers have developed highly active catalysts consisting of bulky, electron-rich phosphine ligands with a biphenyl backbone combined with Pd(OAc)2 for the arylation of ketones or nitroalkanes (Eq. 5.72).115

5.7 INTRODUCTION OF HETEROATOMS TO NITROALKANES

The anion derived from nitroalkanes react with various electrophiles to give α-hetero-substituted nitroalkanes (Scheme 5.15).116 Halogenation of nitroalkanes is especially well known and very

152 ALKYLATION, ACYLATION, AND HALOGENATION OF NITRO COMPOUNDS

Ring cleavage often represents a particularly effective route to α,ω-difunctionalized frameworks. As discussed in Section 5.4, 2-nitrocyclocycloalkanones are able to produce a consistent array of functionalized molecules through an easy nucleophilic retro-Claisen condensation. Treatment of 2-nitrocycloalkanones with basic solution of sodium hypochlorite leads to the formation of ω,ω-dichloro-ω-nitroalkanoic acids. The ring cleavagebromination with NBS and MeONa in MeOH leads to the formation of the corresponding bromides. The reaction of these halides with allylstannane in the presence of AIBN gives

the denitro-allylated or debromo-allylated products, depending on the halides, as shown in Eq. 5.77.123

Indium-mediated reductive cyclization of 2-nitroacylbenzenes into 2,1-benzisoxazoles in

aqueous media is catalyzed by the presence of 2-bromo-2-nitropropane (Eq. 5.78).124 The mechanism is not clear yet; the electron transfer to 2-bromo-2-nitropropane may induce the reduction.

The potassium salts of nitro compounds are fluorinated on treatment with FClO3, but it is

still troublesome to handle the fluorinating agents. Safer methods are highly desired (Eq.

5.79).125,126

α-Nitrosulfides have been often used in organic synthesis, especially (phenylthio)ni-

tromethane, which is a convenient reagent for synthesis of furan, for preparation of α-substituted thiol esters via the Michael addition followed by the Nef reaction and for the preparation of β-lactam.127 This useful reagent is prepared by sulfenylation of nitromethane with phenysulfenyl chloride (Eq. 5.80).128 Alternatively, this reagent may be prepared from the nitration of the dianion derived from (phenylthio)acetic acid.129

In a similar way, α-nitroselenides are prepared via the reaction of nitronates with phenylselenyl bromide, which gives a new synthetic method of 1-nitroalkenes from nitroalkanes.130 The sequence of α-selenation, nitro-aldol reaction, and oxidation provides a useful method for the preparation of nitroalkenes with a hydroxymethyl group (Eq. 5.81).131

(5.81)

This strategy is applied to a general method for the preparation of 2,2-disubstituted 1-ni- troalkenes. Conjugate 1,4-addition of complex zinc cuprates to 1-nitroalkenes, followed by trapping with phenylselenyl bromide and subsequent oxidative elimination, affords the corresponding 2,2-disubstituted 1-nitroalkenes in good yields (Eq. 5.82).132

The review by Barrett (Ref. 127) documents synthetic application of hetero-substituted nitroalkenes (see also Chapter 4). 1-Chloro-1-nitroalkenes are readily obtained either by the Henry reaction of chloronitromethane with aldehydes or chlorination of 1-nitroalkenes. Dauzonne and coworkers have used 1-chloro-1-nitroalkenes for construction of dihydrobenzofuran or dihydrobenzopyran frameworks. (Eq. 5.83).133

α-Nitro ethers are difficult to prepare due to their instability. However, Vassella and co-workers have succeeded in preparation of deoxy-nitrosugars. Ozonolysis of N-glycosylni- trones obtained from the corresponding oximes affords 1-deoxy-1-nitroaldose (Eq. 5.84).134 They have developed new reactions and intermediates using 1-deoxy-1-nitroaldose, as summarized in Scheme 5.19.135 α-Nitroethers are good precursors of alkyl radicals or carbenium ions stabilized by the oxygen atom. Details of the reactions in Scheme 5.19 are discussed in Chapter 7.

154 ALKYLATION, ACYLATION, AND HALOGENATION OF NITRO COMPOUNDS

OR

OR

Scheme 5.19.

REFERENCES

1.Hass, H. B., and M. L. Bender. Org. Synth., ", 932 (1963).

2.Zen, S., and E. Kaji. Org. Synth., $, 503 (1988).

3.Zen, S., M. Koyama, and S. Koto. Org. Synth., $, 797 (1988).

4.Sylvan, C., A. Wagner, and C. Mioskowski. Tetrahedron Lett, " , 875 (1999).

5.Niyazymbetov, M. E., and D. H. Evans. J. Org. Chem., #&, 779 (1993).

6.Wade, P. A., H. R. Hinney, N. V. Amin, P. D. Vail, S. D. Morrow, S. A. Hardinger, and M. S. Saft . J. Org. Chem., "$, 765 (1981).

7.Kornblum, N., S. D. Boyd, and N. Ono. J. Am. Chem. Soc., '$, 2580 (1974).

12.Seebach, D., R. Henning, and T. Mukhopadhyay. Chem. Ber., #, 1705 (1982).

13.Ballini, R., E. Marcantoni, and M. Petrini. Liebigs Ann., 1381 (1995).

16.Shipchandler, M. T. Synthesis, 666 (1979).

17.Rene, L., and R. Royer. Synthesis, 878 (1981).

21.Faulques, M., L. Rene, and R. Royer. Synthesis, 260 (1982).

22.Ono, N., M. Fujii, and A. Kaji. Synthesis, 532 (1987).

23.Fied, G. F., and W. J. Zally. Synthesis, 295 (1979).

24. Hamada, Y., K. Ando, and T. Shioiri. Chem. Pharm. Bull., ', 259 (1981).

25.Jager, V., B. Seidel, and E. Guntrum. Synthesis, 629 (1991).

26.Nudelman, A., and A. Nudelman. Synthesis, 568 (1999).

REFERENCES 155

29.Fisher, R. H., and H. M. Weitz. Synthesis, 26 (1981).

30.Ballini, R., M. Petrini, and V. Polzonetti. Synthesis, 355 (1992).

31.Ballini, R., G. Bosica, and F. Gigli. Tetrahedron, #", 7573 (1998).

32.Ballini, R., M. Petrini, and G. Rosini. Tetrahedron, "$, 16131 (1990).

33.Ballini, R., M. Curini, F. Epifano, M. C. Marcotullio, and O. Rosanti. Synlett, 1049 (1998).

34.Ballini, R., G. Bartoli, P. V. Gariboldi, E. Marcantoni, and M. Petrini. J. Org. Chem., #&, 3368 (1993).

35.Ballini, R., G. Bartoli, R. Giovannini, E. Marcantoni, and M. Petrini. Tetrahedron Lett., !", 3301 (1993).

36.Ballini, R., L. Barboni, and L. Pintucci. Synlett, 1839 (1997).

43.Kornblum, N., and M. J. Fifolt. J. Org. Chem., "#, 361 (1980).

44.Ros, F., and J. D. L. Rosa. J. Org. Chem., #!, 2868 (1988).

45.Kornblum, N., W. J. Kelley, and M. M. Kestner. J. Org. Chem., # , 4720 (1985).

46.Kornblum, N., S. D. Boyd, and N. Ono. J. Am. Chem. Soc., '$, 2580 (1974).

47.Kornblum, N., S. D. Boyd, and F. W. Stuchal. J. Am. Chem. Soc., ' , 5783 (1970).

48.Kornblum, N., H. K. Singh, and S. D. Boyd. J. Org. Chem., "', 358 (1984).

49.Kornblum, N., and A. S. Erickson. J. Org. Chem., "$, 1039 (1981).

53.Beraud, V., P. Perfetti, C. Pfister, M. Kaffarani, P. Vanelle, and M. P. Crozet. Tetrahedron, #", 4923 (1998).

54. Beugelmans, R., T. Frinault, and A. Lechevarllier. Tetrahedron Lett., ', 2567 (1988).

55.Vanelle, P., A. Gellis, M. Kaafarani, J. Maldonado, and M. P. Crozet. Tetrahedron Lett., " , 4343 (1999).

156 ALKYLATION, ACYLATION, AND HALOGENATION OF NITRO COMPOUNDS

59d. Katritzky, A. R., M. A. Kashmiri, and D. K. Wittmann. Tetrahedron, " , 1501 (1984). 60a. Kurz, M. E., and T. Y. R. Chen. J. Org. Chem., "!, 239 (1978).

60b. Kurz, M. E., P. Ngoviwatchai, and T. Tantrarant. J. Org. Chem., "$, 4668 (1981). 61a. Arai, N., and K. Narasaka. Chem. Lett., 987 (1995).

61b. Arai, N., and K. Narasaka. Bull. Chem. Soc. Jpn., % , 2525 (1997).

62.Durand, A. C., E. Dumez, J. Rodriguez, and J. P. Dulcere. Chem. Commun., 2437 (1999).

63.Durand, A. C., J. Rodrigez, and J. P. Dulcere. Synlett, 731 (2000).

64.Bowman, W. R., and S. W. Jackson. Tetrahedron, "$, 7313 (1990).

65.Adebayo, A. T. O. M., W. R. Bowman, and W. G. Salt. J. Chem. Soc., Perkin Trans 1 1415 (1989).

66.Takahashi, Y., M. Tokuda, M. Itoh, and A. Suzuki. Synthesis, 616 (1976).

67.Wrobel, Z. Pol. J. Chem., $&, 2613 (1994).

68a. Heck, R. F. Palladium Reagents in Organic Synthesis, Academic Press, 1985.

68b. Tsuji, J. Palladium Reagents and Catalysts, Innovations in Organic Synthesis, John Wiley & Sons, 1995.

69. Jolly, P. W. Angew. Chem. Int. Ed. Engl., ", 283 (1985).

70.Mitsuyasu, T., and J. Tsuji. Tetrahedron, ! , 831 (1974).

71.Takahashi, T., S. Hasiguchi, K. Kasuga, and J. Tsuji. J. Am. Chem. Soc., , 742 (1978).

72.Takacs, J. M., and J. Zhu. J. Org. Chem., #", 5193 (1989).

73.Larock, R. C., and C. A. Fried. J. Am. Chem. Soc., , 5882 (1990).

74.Hegedus, L. S., and R. J. Perry. J. Org. Chem., "', 2570 (1984).

75a. Wade, P. A., S. Morrow, and S. Hardinger. J. Org. Chem., "%, 365 (1982). 75b. Aleksandrowicz, P., H. Piotrowska, and W. Sas. Tetrahedron, !&, 1321 (1982).

76.Wade, P. A., H. R. Hinne, N. V. Amin, P. D. Vail, S. D. Morrow, S. A. Hardinger, and M. S. Saft. J. Org. Chem., "$, 765 (1981).

77.Tsuji, J., I. Shimizu, I. Minami, Y. Ohashi, T. Sugiura, and K. Takahashi. J. Org. Chem., # , 1523 (1985).

82.Lalonde, J. J., D. E. Bergbreiter, and C. H. Wong. J. Org. Chem., #!, 2323 (1988).

83.Manjunatha, S. G., P. Chittari, and S. Rajappa. Helv. Chim. Acta., %", 1071 (1991).

84.Manjunatha, S. G., K. V. Reddy, and S. Rajappa. Tetrahedron Lett., ! , 1327 (1990). 85a. Chittari, P., A. Thomas, and S. Rajappa. Tetrahedron Lett., !#, 3793 (1994).

85b. Thomas, A., and D. Rajappa. Tetrahedron, # , 10571 (1995). 86a. Ritter, A. R., and M. J. Miller. J. Org. Chem., #', 4602 (1994). 86b. Ghosh, A., and M. J. Miller. Tetrahedron Lett., !$, 6399 (1995).

87.Zhang, D., A. Ghosh, C. Suling, and M. J. Miller. Tetrahedron Lett., !%, 3799 (1996). 88a. Park, K. H., and H. Rapopport. J. Org. Chem., #', 394 (1994).

88b. Peel, M. P., D. D. Sternbach, and M. R. Johnson. J. Org. Chem., #$, 4990 (1991).

89.Zhang, D., and M. J. Miller. J. Org. Chem., $!, 755 (1998).

90.Trost, B. M., and D. L. V. Vranken. Chem. Rev., '$, 395 (1996).

91.Trost, B. M., D. Stenkamp, and S. R. Pulley. Chem. Eur. J. , 568 (1995).

92a. Trost, B. M., G. H. Kuo, and T. Benneche. J. Am. Chem. Soc., , 621 (1988). 92b. Trost, B. M., L. Li, and S. D. Guile. J. Am. Chem. Soc., ", 8745 (1992).

96.Pfaltz, A. Synlett., 835 (1999).

97.Deardorf, D. R., C. Q. Windham, and C. L. Craney. Org. Synth., ', 487 (1998).

98.Schink, H. E., and J. E. Backvall. J. Org. Chem., #%, 1588 (1992).

99.Tamura, R., H. Shimizu, N. Ono, N. Azuma, and H. Suzuki. Organometallics, , 954 (1992).

REFERENCES 157

100.Terrier, F. Nucleophilic Aromatic Displacement. The Influence of the Nitro Group,VCH, New York, 1991.

106.Barton, D. H. R., J. C. Blazejewski, B. Charpiot, D. J. Lester, W. B. Motherwell, and M. T. B. Papoula. J. Chem. Soc. Chem. Commun., 827 (1980).

107.Fornicola, R. S., E. Oblinger, and J. Montgomery. J. Org. Chem. $!, 6328 (1998).

108.Arnauld, T., D. H. R. Barton, J. F. Normant, and E. Doris. J. Org. Chem., $", 6915 (1999). 109a. Kozyrod, R. P., and J. T. Pinhey. Org. Synth., %, 229 (1990).

109b. Kozyrod, R. P., and J. T. Pinhey. Aust. J. Chem., !&, 713 (1985).

112.Moriarty, R. M., and R. K. Vaid. Synthesis, 431 (1990).

113.Kornblum, N., and H. J. Taylor. J. Org. Chem., &, 1424 (1963).

114.Muratake, H., and H. Nakai. Tetrahedron Lett., " , 2355 (1999).

117.Kornblum, N., M. M. Kestner, S. D. Boyd, and L. C. Cattran. J. Am. Chem. Soc., '#, 3345 (1973).

118.Bowman, W. R. Chem. Soc. Rev., %, 283 (1988).

119a. Fishwick, B. R., D. K. Bowles, and C. J. M. Stirling. J. Chem. Soc., Chem. Commun., 834 and 835 (1983).

119b. Fishwick, B. R., D. K. Bowles and C. J. M. Stirling. J. Chem. Soc. Perkin Trans 1, 1171 (1986).

120.Norris, T., T. F. Braish, M. Butters, K. M. DeVries, J. M. Hawkins, S. S. Massert, P. R. Rose, D. Santafianos, and C. Sklavounos. J. Chem. Soc., Perkin Trans 1, 1615 (2000).

121.Brightly, K. E., and T. D. Gootz. Med. Res. Rev., $, 433 (1996).

122.Ono, N., K. Zinsmeister, and A. Kaji. Bull. Chem. Soc. Jpn., #&, 1069 (1985).

123.Ballini, R., M. Petrini, and O. Polimanti. J. Org. Chem., $ , 5652 (1996).

124.Kim, B. H., Y. Jin, Y. M. Jun, R. Han, W. Baik, and B. M. Lee. Tetrahedron Lett., " , 2137 (2000).

125.Takeuchi, Y., H. Ogura, A. Kanada, and T. Koizumi. J. Org. Chem., #%, 2196 (1992).

126.Adolph, H. G., and W. M. Koppers. Aliphatic Fluoronitro Compounds, in Nitro compounds, ed. by H. Feuer and A. T. Nielsen, VCH, New York, 1990.

127. Barrett, A. G. M. Chem. Soc. Rev., , 95 (1991).

128.Barrett, A. G. M., D. Dhanak, G. G. Graboski, and S. J. Taylor. Org. Synth., &, 550 (1993).

129.Miyashita, M., T. Kumazawa, and A. Yoshikoshi. J. Org. Chem., "#, 2945 (1980).

130.Sakakibara, T., I. Takai, E. Ohara, and R. Sudoh. J. Chem. Soc., Chem. Commun., 261 (1981).

131.Sakakibara, T., S. Ikuta, and R. Sudoh. Synthesis, 261 (1982).

132.Denmark, S. E., and L. R. Marcin. J. Org. Chem., #&, 3850 (1993).

133a. Dauzonne, D., and R. Royer. Synthesis, 1020 (1987).

133b. Dauzonne, D., and R. Royer. Synthesis, 339 (1988).

158 ALKYLATION, ACYLATION, AND HALOGENATION OF NITRO COMPOUNDS

133c. Dauzonne, D., and P. Demerseman. Synthesis, 66 (1990).

133d. Dauzonne, D., H. Josien, and P. Demerseman. Tetrahedron, "$, 7359 (1990). 133e. Dauzonne, D., and C. Grandjean. Synthesis, 677 (1992).

134.Aebischer,. B., and A. Vasella. Helv. Chim. Acta, $$, 789 (1983).

135.Vasella, A., Pure & Appl. Chem., $!, 507 (1991).