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

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synthesis 2004(10): 1563-1565
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

Further Information

Publication History

Received 23 February 2004
Publication Date:
16 June 2004 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

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

References

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

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

Google Scholar
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

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

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

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

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

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

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

Crossref Google Scholar
4 Smith JG. Synthesis 1984, 629

Article in Thieme Connect Google Scholar
5a Overman LE. Flippin LA. Tetrahedron Lett. 1981, 22: 195

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Crossref Google Scholar
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

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

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

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

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

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

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

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

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

Google Scholar
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

Google Scholar
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.

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

Crossref Google Scholar
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

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

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

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

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

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

Article in Thieme Connect Google Scholar
15b O’Niel IA. Cleator E. Southern JM. Hone N. Tapolczay DJ. Synlett 2000, 695

Article in Thieme Connect Google Scholar
15c O’Niel IA. Cleator E. Hone N. Southern JM. Tapolczay DJ. Synlett 2000, 1408

Article in Thieme Connect Google Scholar
16a Kotsuki H. Hayashida K. Shimanouchi T. Nishizawa H. J. Org. Chem. 1996, 61: 984

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

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

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

Google Scholar