Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide†

doi:10.7503/cjcu20130535

Abstract

Abstract:

A novel halolactonization of pentenoic acids was developed, which was catalyzed by hypervalent iodine species generated in situ from ammonium iodide. In this protocol, 4-pentenoic acids reacted easily with lithium bromide or lithium chloride under catalyst ammonium iodide in combination with m-chloroperbenzoic acid(mCPBA) as the terminal oxidant in CH₃CN at room temperature, which provided five-membered halolactones in moderate to good yields. A new plausible reaction pathway for the reaction was hypothesized. Thus, NH₄I was first oxidized to I₂ and HOI with mCPBA, both of them reacted with alkenoic acid to form the iodolactone, which then was transformed into the hypervalent iodine intermediate in situ by the continuing oxidation, and finally the halolactone was provided when lithium bromide or lithium chloride was acted as nucleophile in the following intermolecular nucleophilic substitution. This method has some advantages such as mild reaction conditions, simple procedure and good yields. Furthermore, the scope of hypervalent iodine reagents in organic synthesis could be extended.

Key words: Catalytic halolactonization, Hypervalent iodine intermediate, Ammonium iodide, 4-Pentenoic acid

CLC Number:

O621.3

TrendMD:

ZHU Min, JIN Jianchang, ZHANG Hui. Halolactonization of Alkenoic Acid Catalyzed by Ammonium Iodide^†[J]. Chem. J. Chinese Universities, 2014, 35(2): 286.

Figures/Tables 5

References 41

[1]	Dowle M. D., Davies D. I., Chem. Soc. Rev., 1979, 8, 171—197
[2]	Rousseau G., Robin S., Tetrahedron, 1998, 54, 13681—13736
[3]	van Tamelen E. E., Shamma M., J. Am. Chem. Soc., 1954, 76, 2315—2317
[4]	Anaral L., Melo S. C., J. Org. Chem., 1973, 38, 800—802
[5]	Cambie R.C., Rutledge P. S., Somerville R. F., Woodgate P. D.,Synthesis, 1988, 1009—1014
[6]	Garratt D. G., Ram M. D., Beaulieu P. L., J. Org. Chem., 1980, 45, 839—845
[7]	Mellegaard S. R., Tunge J. A., J. Org. Chem., 2004, 69, 8979—8981
[8]	Mellegaard-Waetzig S. R., Wang C., Tunge J. A., Tetrahedron, 2006, 62, 7191—7198
[9]	Cheng Y. A., Chen T., Tan C. K., Heng J. J., Yeung Y. Y., J. Am. Chem. Soc., 2012, 134, 16492—16495
[10]	Braddock D.C., Cansella G., Hermitage S. A.,Chem. Commun., 2006, 2483—2485
[11]	Goodman M. A., Detty M. R., Organometallics, 2004, 23, 3016—3020
[12]	Bennett S. M., Tang Y., McMaster D., Bright F. V., Detty M. R., J. Org. Chem., 2008, 73, 6849—6852
[13]	Detty M. R., Higgs D. E., Nelen M. I., Org. Lett., 2001, 3, 349—352
[14]	Damin B., Forestiere A., Garapon J., Sillion B., J. Org. Chem., 1981, 46, 3552—3554
[15]	Lopez-Lopez J. A., Guerra F. M., Moreno-Dorado F. J., Jorge Z. D., Massanet G. M., Tetrahedron Lett., 2007, 48, 1749—1752
[16]	Mellegaard S. R., Tunge J. A., J. Org. Chem., 2004, 69, 8979—8981
[17]	Whitehead D. C., Yousefi R., Jaganathan A., Borhan B., J. Am. Chem. Soc., 2010, 132, 3298—3300
[18]	Ho P. T., Davies N., J. Org. Chem., 1984, 49, 3027—3029
[19]	Lewis T. A., Bayless L., Eckman J. B., Ellis J. L., Grewal G., Libertine L., Nicolas J. M., Scannell R. T., Wels B.F., Wenberg K., Wypij D. M., Bioorg. Med. Chem. Lett., 2004, 14, 2265—2268
[20]	Stang P. J., Zhdankin V. V., Chem. Rev., 1996, 96, 1123—1178
[21]	Varvoglis A., Tetrahedron, 1997, 53, 1179—1255
[22]	Zhdankin V. V., Stang P. J., Chem. Rev., 2002, 102, 2523—2584
[23]	Zhdankin V. V., Stang P. J., Chem. Rev., 2008, 108, 5299—5358
[24]	Braddock D.C., Cansella G., Hermitage S. A.,Synlett., 2004, 461—464
[25]	He Y., Yang Z.P., Yan J.,J. Chem. Res., 2010, 167—169
[26]	Richardson R. D., Wirth T., Angew. Chem. Int. Ed., 2006, 45, 4402—4404
[27]	Dohi T., Kita Y.,Chem. Commun., 2009, 2073—2085
[28]	Ochiai M., Chem. Rec., 2007, 7, 12—23
[29]	Uyanik M., Ishihara K.,Chem. Commun., 2009, 2086—2099
[30]	Fang Y. G., Xu C., Zhu M., Chem. J. Chinese Universities, 2011, 32(12), 2782—2786
	(方应国, 徐翠, 朱敏.高等学校化学学报,2011, 32(12), 2782—2786)
[31]	He Y., Pu Y., Shao B.,Yan J., J. Heterocyclic. Chem., 2011, 48, 695—698
[32]	Hossain M.D., Oyamada J., Kitamura T.,Synthesis, 2008, 690—692
[33]	Ganguly N.C., Baric S. K., Dutta S.,Synthesis, 2010, 1467—1472
[34]	Merritt E. A., Olofsson B., Angew. Chem. Int. Ed., 2009, 48, 9052—9070
[35]	Zhu M., Li L., Zhang H., Liu C. Q., Chem. J. Chinese Universities, 2012, 33(9), 1995—1999
	(朱敏, 李立, 张慧, 刘彩琴.高等学校化学学报,2012, 33(9), 1995—1999)
[36]	Uyanik M., Okamoto H., Yasui T., Ishihara K., Science, 2010, 328, 1376—1379
[37]	Tanaka A., Moriyama K., Togo H.,Synlett., 2011, 1853—1858
[38]	Marri M. R., Macharla A. K., Paraka S., Nama N., Tetrahedron Lett., 2011, 52, 6554—6559
[39]	Maslak V., Matovic R., Saicic R. N., Tetrahedron, 2004, 60, 8957—8966
[40]	Ohta H., Sakata Y., Takeuchi T., Ishii Y.,Chem. Lett., 1990, 733—736
[41]	Kang Y. B., Gade L. H., J. Org. Chem., 2012, 77, 1610—1615

Entry	n(LiBr)/mmol	n(NH₄I)/mmol	n(mCPBA)/mmol	Solvent	Time/h	Yield^b(%)
1	1.5	0.1	2.0	CH₂Cl₂	10	45
2	1.5	0.1	2.0	CH₃OH	10	23
3	1.5	0.1	2.0	THF	10	52
4	1.5	0.1	2.0	CF₃CH₂OH	10	67
5	1.5	0.1	2.0	CH₃CN	10	71
6	2.0	0.1	2.0	CH₃CN	10	78
7	3.0	0.1	2.0	CH₃CN	10	79
8	5.0	0.1	2.0	CH₃CN	10	80
9	KBr(2.0)	0.1	2.0	CH₃CN	10	65
10	NaBr(2.0)	0.1	2.0	CH₃CN	10	48
11	NH₄Br(2.0)	0.1	2.0	CH₃CN	10	52
12	2.0	0.2	2.0	CH₃CN	10	77
13	2.0	0.3	2.0	CH₃CN	10	79
14	2.0	0.05	2.0	CH₃CN	10	65
15	2.0	0	2.0	CH₃CN	10	0
16	2.0	KI(0.1)	2.0	CH₃CN	10	51
17	2.0	NaI(0.1)	2.0	CH₃CN	10	63
18	2.0	I₂(0.1)	2.0	CH₃CN	10	66
19	2.0	0.1	NaBO₃(2.0)	CH₃CN	10	5
20	2.0	0.1	Na₂S₂O₈(2.0)	CH₃CN	10	7
21	2.0	0.1	Oxone(2.0)	CH₃CN	10	55
22	2.0	0.1	2.5	CH₃CN	10	84
23	2.0	0.1	3.0	CH₃CN	10	82
24	2.0	0.1	1.5	CH₃CN	10	66
25	2.0	0.1	2.5	CH₃CN	16	85
26	2.0	0.1	2.5	CH₃CN	8	84
27	2.0	0.1	2.5	CH₃CN	6	84
28	2.0	0.1	2.5	CH₃CN	3	68

Entry	n(LiBr)/mmol	n(NH₄I)/mmol	n(mCPBA)/mmol	Solvent	Time/h	Yield^b(%)
1	1.5	0.1	2.0	CH₂Cl₂	10	45
2	1.5	0.1	2.0	CH₃OH	10	23
3	1.5	0.1	2.0	THF	10	52
4	1.5	0.1	2.0	CF₃CH₂OH	10	67
5	1.5	0.1	2.0	CH₃CN	10	71
6	2.0	0.1	2.0	CH₃CN	10	78
7	3.0	0.1	2.0	CH₃CN	10	79
8	5.0	0.1	2.0	CH₃CN	10	80
9	KBr(2.0)	0.1	2.0	CH₃CN	10	65
10	NaBr(2.0)	0.1	2.0	CH₃CN	10	48
11	NH₄Br(2.0)	0.1	2.0	CH₃CN	10	52
12	2.0	0.2	2.0	CH₃CN	10	77
13	2.0	0.3	2.0	CH₃CN	10	79
14	2.0	0.05	2.0	CH₃CN	10	65
15	2.0	0	2.0	CH₃CN	10	0
16	2.0	KI(0.1)	2.0	CH₃CN	10	51
17	2.0	NaI(0.1)	2.0	CH₃CN	10	63
18	2.0	I₂(0.1)	2.0	CH₃CN	10	66
19	2.0	0.1	NaBO₃(2.0)	CH₃CN	10	5
20	2.0	0.1	Na₂S₂O₈(2.0)	CH₃CN	10	7
21	2.0	0.1	Oxone(2.0)	CH₃CN	10	55
22	2.0	0.1	2.5	CH₃CN	10	84
23	2.0	0.1	3.0	CH₃CN	10	82
24	2.0	0.1	1.5	CH₃CN	10	66
25	2.0	0.1	2.5	CH₃CN	16	85
26	2.0	0.1	2.5	CH₃CN	8	84
27	2.0	0.1	2.5	CH₃CN	6	84
28	2.0	0.1	2.5	CH₃CN	3	68