A New and Efficient Epoxide Ring Opening via Poor Nucleophiles: Indole, p-Nitroaniline, Borane and O-Trimethylsilylhydroxylamine in Lithium Perchlorate

Akbar Heydari; Morteza Mehrdad; Aziz Maleki; Nafiseh Ahmadi

doi:10.1055/s-2004-822406

SHORTPAPER

A New and Efficient Epoxide Ring Opening via Poor Nucleophiles: Indole, p-Nitroaniline, Borane and O-Trimethylsilylhydroxylamine in Lithium Perchlorate

Akbar Heydari*^a, Morteza Mehrdad^b, Aziz Maleki^a, Nafiseh Ahmadi^a
^a Chemistry Department, Tarbiat Modarres University, P. O. Box 14155-4838, Tehran, Iran
Fax: +98(21)8006544; e-Mail: akbar.heydari@gmx.de;
^b Department of Phytochemistry, Shahid Beheshti University, Evin 1983963113, Tehran, Iran

Abstract

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Abstract

Highly regioselective ring opening of 2,3-dimethyloxirane, 2-epoxyphenylether and allyl(2-epoxymethyl) ether are observed through reactions with poor nucleophiles such as indole, borane, O-trimethylsilylhydroxylamine, p-nitroaniline and sterically hindered tert-butylamine in the presence of 5.0 M lithium perchlorate-Et₂O solution. These reactions are fast, convenient, with rather high yields and are carried out at ambient temperatures.

Key words

lithium perchlorate - epoxide - β-amino alcohols

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Referenzen

References

1a Moller F. In Methoden der Organische Chemie (Houben-Weyl) Vol 11/1, 4th ed.: Thieme Verlag; Stuttgart: 1957. p.311-326

1b Mitsunobu O. In Comprehensive Organic Synthesis Vol. 6: Trost BM. Fleming I. Pattenden G. Pergamon; Oxford: 1991. p.88-93

1c Birkinshaw TN. In Comprehensive Organic Functional Group Transformations Vol. 1: Katritzky AR. Meth-Cohn O. Rees CW. Roberts SM. Pergamon Press; Oxford: 1990. p.204-220

2a Hanson RM. Chem. Rev. 1991, 91: 437

2b Hodgson DM. Gibbs AR. Lee GP. Tetrahedron 1996, 52: 14361

2c Rao AS. Paknikar SK. Kirtane JG. Tetrahedron 1983, 39: 2323

3a Corey EJ. Zhang F. Angew. Chem. Int. Ed. 1999, 38: 1931

3b Roger GA. Parsons SM. Anderson DC. Nilsson Bahr BA. Korneich WD. Kaufman R. Jacobs RS. Kitman B. J. Med. Chem. 1989, 32: 1217

3c Chang BL. Ganesan A. Bioorg. Med. Chem. Lett. 1997, 7: 1511

4 Smith JG. Synthesis 1984, 629

5a Overman LE. Flippin LA. Tetrahedron Lett. 1981, 22: 195

5b Overman LE. Fukaya C. J. Am. Chem. Soc. 1980, 102: 1454

5c Deyrup JA. Moher CL. J. Org. Chem. 1969, 34: 175

5d Crooks PA. Szyndler R. Chem. Ind. (London) 1973, 1111

6 Iqbal J. Pandey A. Tetrahedron Lett. 1990, 31: 575

7 Das U. Crousse B. Kesavan V. Bonnet-Delpon D. Begue J.-P. J. Org. Chem. 2000, 65: 6749

8 Sagava S. Abe H. Hase Y. Inaba T. J. Org. Chem. 1999, 64: 4962

9a Van de Weghe P. Collin J. Tetrahedron Lett. 1995, 36: 1649

9b Fu X.-L. Wu S.-H. Synth. Commun. 1997, 27: 1677

10a Cossy J. Bellosta V. Hamoir C. Desmurs J.-R. Tetrahedron Lett. 2002, 43: 7083

10b Sekar G. Sing VK. J. Org. Chem. 1999, 64: 287

10c Auge J. Leroy F. Tetrahedron Lett. 1996, 37: 7715

10d Sagava S. Abe H. Hase Y. Inaba T. J. Org. Chem. 1999, 64: 4962

10e Meguro M. Asao N. Yamamoto Y. J. Chem. Soc., Perkin Trans. 1 1994, 2597

10f Chini M. Crotti P. Favero L. Macchia F. Pineschi M. Tetrahedron Lett. 1994, 35: 433

10g Fujiwara M. Imada M. Baba A. Matsuda H. Tetrahedron Lett. 1989, 30: 739

11a Carre MC. Houmounou JP. Caubere P. Tetrahedron Lett. 1985, 26: 3107

11b Kissel CL. Rickborn B. J. Org. Chem. 1972, 37: 2060

11c Overman LE. Flippin LA. Tetrahedron Lett. 1981, 22: 195

11d Yamada J.-I. Yumoto M. Yamamoto Y. Tetrahedron Lett. 1989, 30: 4255

11e Fiorenza M. Ricci A. Taddei M. Tassi D. Seconi G. Synthesis 1983, 640

11f Papini A. Ricci A. Taddei M. Seconi G. Dembech P. J. Chem. Soc., Perkin Trans. 1 1984, 2261

11g Atkins RK. Fazier J. Moore LL. Weigel LO. Tetrahedron Lett. 1986, 27: 2451

It is worth noting that LiClO₄ was used as a promoter in epoxide opening reaction with nucleophiles:

12a Chini M. Crotti P. Gardelli C. Macchia F. Synlett 1992, 673

12b Chini M. Crotti P. Giovani E. Macchia F. Pineschi M. Synlett 1992, 303

12c Chini M. Crotti P. Flippin LA. Macchia F. J. Org. Chem. 1991, 56: 7043

12d Chini M. Crotti P. Pineschi M. Tetrahedron Lett. 1991, 32: 7583

12e Chini M. Crotti P. Macchia F. J. Org. Chem. 1991, 56: 5939

12f Chini M. Crotti P. Macchia F. Tetrahedron Lett. 1990, 31: 4661

12g Chini M. Crotti P. Favero L. Macchia F. Tetrahedron Lett. 1991, 32: 4775

12h Chini M. Crotti P. Macchia F. Tetrahedron Lett. 1990, 31: 5641

12i Chang BL. Ganesan A. Bioorg. Med. Chem. Lett. 1997, 7: 1511

12j However, to the best of our knowledge, lithium perchlorate-Et₂O solution (5.0 M) has been used in epoxide ring opening only with silylated nucleophiles: Ipaktschi J. Heydari A. Chem. Ber. 1993, 126: 1905

12k

For the sake of comparison we first investigated the aminolysis of 1,2-epoxy-3-phenoxypropane under the conditions described by Crotti. When the reaction of diethylamine with an epoxide was conducted in the presence of 2 equiv of lithium perchlorate, the conversion went for 1-diethylamino-2-hydroxy-3-phenoxypropane to 60% after 3 h. In 5.0 M LPDE the reaction was complete (97% yield) after 30 min at r.t. In addition when 1,2-epoxy-3-phenoxypropane was treated with 2-phenylethylamine and LiClO₄ in CH₂Cl₂ the ring opening product was obtained in inferior to 40% yield even with 2 equiv of LiClO₄, 10 equiv of amine and heating.

13a For a review see: Heydari A. Tetrahedron 2002, 58: 6777

13b Recently, Yadav reported several useful synthetic reactions which proceed smoothly in highly concentrated LPDE: Yadav JS. Reddy BVS. Shesha Rao M. Reddy PN. Tetrahedron Lett. 2003, 44: 5275

13c Yadav JS. Reddy BVS. Narsimhaswamy D. Narsimulu K. Kunwar AC. Tetrahedron Lett. 2003, 44: 3697

14a Jordan S. Markwell RE. Woolcott BS. J. Chem. Soc., Perkin Trans. 1 1978, 928

14b Malinovskii MS. Martyushenko VA. Chem. Abstr. 1966, 64: 625

14c Zinner G. Ritter AW. Angew. Chem. 1962, 74: 21

15a O’Niel IA. Southern JM. Tetrahedron Lett. 1998, 39: 9089

15b O’Niel IA. Cleator E. Southern JM. Hone N. Tapolczay DJ. Synlett 2000, 695

15c O’Niel IA. Cleator E. Hone N. Southern JM. Tapolczay DJ. Synlett 2000, 1408

16a Kotsuki H. Hayashida K. Shimanouchi T. Nishizawa H. J. Org. Chem. 1996, 61: 984

16b Kotsuki H. Nishiuchi M. Kobayashi S. Nishizawa H. J. Org. Chem. 1990, 55: 2969

16c Bandini M. Cozzi PG. Melchiorre P. Umani-Ronchi A. J. Org. Chem. 2002, 67: 5386

17 Dirlam JP. Clark DA. Hecker SJ. J. Org. Chem. 1986, 51: 4920