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DOI: 10.1055/s-2007-965927
Regioselectivity in a Highly Efficient, Microwave-Assisted Epoxide Aminolysis
Publication History
Publication Date:
08 February 2007 (online)
Abstract
We have developed a microwave-assisted aminolysis of epoxides as an efficient method for synthesizing a number of β-amino alcohols. In most cases, including in reactions of amines with a trisubstituted epoxide, only one equivalent of amine is required to obtain good yields. The reactions are consistently regioselective for amine nucleophiles of varying strengths and for both hindered and unhindered epoxides. In some cases, this regioselectivity could be enhanced by using a polar aprotic or a non-polar solvent.
Key words
amino alcohols - amines - epoxides - regioselectivity - solvent effects
- 1
Bergmeier SC. Tetrahedron 2000, 56: 2561 ; and references cited therein - 2
Lee H.-S.Kang SH. Synlett 2004, 1673 - For reviews, see:
-
3a
Ager DJ.Prakash I.Schaad DR. Chem. Rev. 1996, 96: 835 -
3b
Kolb HC.Sharpless KB. In Transition Metals for Organic SynthesisBeller M.Bolm C. Wiley-VCH; Weinheim: 1998. p.243 -
3c
Pu L.Yu H.-B. Chem. Rev. 2001, 101: 757 -
3d
de Parrodi AC.Juaristi E. Synlett 2006, 2699 - For recent examples, see:
-
3e
Garcia-Delgado N.Fontes M.Pericas MA.Riera A.Verdaguer X. Tetrahedron: Asymmetry 2004, 15: 2085 -
3f
Castellnou D.Sola L.Jimeno C.Fraile JM.Mayoral JA.Riera A.Pericas MA. J. Org. Chem. 2005, 70: 433 -
3g
Yamashita M.Yamada K.Tomioka K. Org. Lett. 2005, 7: 2369 -
3h
Huang J.Ianni JC.Antoline JE.Hsung RP.Kozlowski MC. Org. Lett. 2006, 8: 1565 -
3i
Schiffers I.Rantanen T.Schmidt F.Bergmans W.Zani L.Bolm C. J. Org. Chem. 2006, 71: 2320 - Two powerful alternate methods for synthesizing β-amino alcohols are the Sharpless aminohydroxylation and the Mannich-type reaction. Aminohydroxylation:
-
4a
Li G.Chang H.-T.Sharpless KB. Angew. Chem. Int. Ed. 1996, 35: 451 -
4b
O’Brien P. Angew. Chem. Int. Ed. 1999, 38: 326 - Mannich-type reaction:
-
4c
Trost BM.Terrell LR. J. Am. Chem. Soc. 2003, 125: 338 ; and references cited therein - 5 For an excellent leading reference listing metal-mediated epoxide aminolyses published through 2001, see:
Cossy J.Bellosta V.Hamoir C.Desmurs J.-R. Tetrahedron Lett. 2002, 43: 7083 - Recent examples:
-
6a LiClO4:
Heydari A.Mehrdad M.Maleki A.Ahmadi N. Synthesis 2004, 1563 -
6b See also:
Azizi N.Saidi MR. Can. J. Chem. 2005, 83: 505 -
6c LiBr:
Chakraborti AK.Rudrawar S.Kondaskar A. Eur. J. Org. Chem. 2004, 3597 -
6d
LiNTf2: see reference 5
-
6e Ca(OTf)2:
Cepanec I.Litvic M.Mikuldas H.Bartolincic A.Vinkovic V. Tetrahedron 2003, 59: 2435 -
6f See also:
Babic A.Sova M.Gobec S.Pecar S. Tetrahedron Lett. 2006, 47: 1733 -
6g Al(OTf)3:
Fringuelli F.Pizzo F.Tortoioli S.Vaccaro L. J. Org. Chem. 2004, 69: 7745 -
6h see also:
Williams DBG.Lawton M. Tetrahedron Lett. 2006, 47: 6557 -
6i BiCl3:
Swamy NR.Kondaji G.Nagaiah K. Synth. Commun. 2002, 32: 2307 -
6j See also:
McCluskey A.Leitch SK.Garner J.Caden CE.Hill TA.Odell LR.Stewart SG. Tetrahedron Lett. 2005, 46: 8229 -
6k Bi(OTf)3 and Bi(TFA)3:
Khodaei MM.Khosropour AR.Ghozati K. Tetrahedron Lett. 2004, 45: 3525 -
6l Sc(OTf)3:
Placzek AT.Donelson JL.Trivedi R.Gibbs RA.De S K. Tetrahedron Lett. 2005, 46: 9029 -
6m ZrCl4:
Chakraborti AK.Kondaskar A. Tetrahedron Lett. 2003, 44: 8315 -
6n CoCl2:
Sundararajan G.Vijayakrishna K.Varghese B. Tetrahedron Lett. 2004, 45: 8253 -
6o Cu(BF4)2:
Kamal A.Ramu R.Azhar MA.Khanna GBR. Tetrahedron Lett. 2005, 46: 2675 -
6p See also:
Yarapathy VR.Mekala S.Rao BV.Tammishetti S. Catal. Commun. 2006, 7: 466 -
6q ZnCl2:
Pachon LD.Gamez P.van Brussel JJM.Reedijk J. Tetrahedron Lett. 2003, 44: 6025 -
6r Yb(OTf)3:
Shi M.Chen Y. J. Fluorine Chem. 2003, 122: 219 -
6s K5CoW12O40·3H2O and (NH4)8[CeW10O36]·20H2O:
Mirkhani V.Tangestaninejad S.Yadollahi B.Alipanah L. Catal. Lett. 2005, 101: 93 -
6t See also:
Rafiee E.Tangestaninejad S.Habibi MH.Mirkhani V. Synth. Commun. 2004, 34: 3673 -
6u Cyclodextrin:
Surendra K.Krishnaveni NS.Rao KR. Synlett 2005, 506 -
6v Silica gel:
Kotsuki H.Hayashida K.Shimanouchi T.Nishizawa H. J. Org. Chem. 1996, 61: 984 -
6w See also:
Chakraborti A.Rudrawar S.Kondaskar A. Org. Biomol. Chem. 2004, 2: 1277 -
6x Montmorillonite K 10:
Chakraborti A.Kondaskar A.Rudrawar S. Tetrahedron 2004, 60: 9085 -
6y [Cr(salen)Cl]:
Bartoli G.Bosco M.Carlone A.Locatelli M.Massaccesi M.Melchiorre Sambri L. Org. Lett. 2004, 6: 2173 -
6z See also:
Kureshy RI.Sing S.Khan N.Abdi SHR.Agrawal S.Jasra RV. Tetrahedron: Asymmetry 2006, 17: 1638 -
6aa Zeolite:
Onaka M.Kawai M.Izumi Y. Chem. Lett. 1985, 779 -
7a
Kotsuki H.Hayakawa H.Wakao M.Shimanouchi T.Ochi M. Tetrahedron: Asymmetry 1995, 6: 2665 -
7b
Kotsuki H.Wakao M.Hayakawa H.Shimanouchi T.Shiro M. J. Org. Chem. 1996, 61: 8915 -
7c
See also refs 6s and 6t.
- 8
Huerta G.Contreras-Ordonez G.Alvarez-Toledano C.Santes V.Gomez E.Toscano RA. Synth. Commun. 2004, 34: 2393 -
9a
Chrisman W.Camara JN.Marcellini K.Singaram B.Goralski CT.Hasha DL.Rudolf PR.Nicholson LW.Borodychuk KK. Tetrahedron 2001, 42: 5805 -
9b
Azizi N.Saidi MR. Org. Lett. 2005, 7: 3649 -
9c
Bonollo S.Fringuelli F.Pizzo F.Vaccaro L. Green Chem. 2006, 8: 960 - For exceptions giving SN1 regioselectivity with better amine nucleophiles, see refs 6p and 8. For SN2 selectivity using poorer nucleophiles, see:
-
10a
Fu X.-L.Wu S.-H. Synth. Commun. 1997, 27: 1677 -
10b
Ref. 6s.
-
11a
Chini M.Crotti P.Favero L.Macchia F.Pineschi M. Tetrahedron Lett. 1994, 35: 433 -
11b
Meguro M.Asao N.Yamamoto Y. J. Chem. Soc., Perkin Trans. 1 1994, 2598 -
11c
Van de Wedghe P.Collin J. Tetrahedron Lett. 1995, 36: 1649 - 13 For a recent example of an alternate approach, see:
Metro T.-X.Appenzeller J.Pardo DG.Cossy J. Org. Lett. 2006, 8: 3509 - For books, see:
-
14a
Microwave Assisted Organic Synthesis
Tierney JP.Lidstrom P. Blackwell; Oxford: 2005. -
14b
Kappe O.Stadler A. Microwaves in Organic and Medicinal Chemistry Wiley-VCH; Weinhiem: 2005. -
14c
Microwaves in Organic Synthesis
Loupy A. Wiley-VCH; Weinheim: 2006. - For reviews, see:
-
15a
Varma RS. Pure Appl. Chem. 2001, 73: 193 -
15b
Perreux L.Loupy A. Tetrahedron 2001, 57: 9199 -
15c
Lidstrom P.Tierney J.Wathey B.Westman J. Tetrahedron 2001, 57: 9225 -
15d
Kuhnert N. Angew. Chem. Int. Ed. 2002, 41: 1863 -
15e
Nuchter M.Ondruschka B.Bonrath W.Gum A. Green Chem. 2004, 6: 128 -
15f
Kappe O. Angew. Chem. Int. Ed. 2004, 43: 6250 -
16a
McCarthy TJ.Dence CS.Welch JM. Appl. Radiat. Isot. 1993, 44: 1129 -
16b
Gupta R.Paul S.Gupta AK.Kachroo PL. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1997, 36: 281 -
16c
Glas H.Thiel WR. Tetrahedron Lett. 1998, 39: 5509 -
16d
Mojtahedi MM.Saidi MR.Bolourtchian M. J. Chem. Res., Synop. 1999, 128 -
16e
Sabitha G.Subba Reddy BV.Abraham S.Yadav JS. Green Chem. 1999, 3: 251 -
16f
Lindstrom UM.Olofsson B.Somfai P. Tetrahedron Lett. 1999, 40: 9273 -
16g
Lindsay KB.Pyne SG. Tetrahedron 2004, 60: 4173 -
16h
Alikhani V.Beer D.Bentley D.Bruce I.Cuenoud BM.Fairhurst RA.Gedeck P.Haberthuer S.Hayden C.Janus D.Jordan L.Lewis C.Smithies E.Wissler E. Bioorg. Med. Chem. Lett. 2004, 14: 4705 -
16i
Eshghi H.Rahimizadeh M.Shoryabi A. Synth. Commun. 2005, 35: 791 -
16j
Rodriquez-Escrich S.Popa D.Jimeno C.Vidal-Ferran A.Pericas MA. Org. Lett. 2005, 7: 3829 -
16k
Sello G.Orsini F.Bernasconi S.Di Gennaro P. Tetrahedron: Asymmetry 2006, 17: 372 -
16l
Schirok H. J. Org. Chem. 2006, 71: 5538 - 17 Bis-alkylation is common in these reactions; see, for example, ref. 6f. For suppression of bis-alkylation in the aminolysis of styrene oxide with primary amines, see:
Randall K.Atkins RK.Frazier J.Moore LL.Weigel LO. Tetrahedron Lett. 1986, 27: 2451 - 18 For an example of solvent-dependent regioselectivity in epoxide aminolysis, see:
Anderson SR.Ayers JT.DeVries KM.Ito F.Mendenhall D.Vanderplas BC. Tetrahedron: Asymmetry 1999, 10: 2655 -
19a
Overman LE.Kakimoto M.Okazaki ME.Meier GP. J. Am. Chem. Soc. 1983, 105: 6622 -
19b
Cooke A.Bennett J.McDaid E. Tetrahedron Lett. 2002, 43: 903 -
19c
See also refs 5 and 6n.
- For examples of regioselectivity for allylamino alcohol 11 via Pd or Rh π-allyl, see:
-
20a
Fagnou K.Lautens M. Org. Lett. 2000, 2: 2319 -
20b
Trost BM.Bunt RC.Lemoine RC.Calkins TL. J. Am. Chem. Soc. 2000, 122: 5968 -
20c
Trost BM.Jiang C.Hammer K. Synthesis 2005, 3335 - 21
Chini M.Crotti P.Macchia F. J. Org. Chem. 1991, 56: 5939 - 22
Kotsuki H.Hayashida K.Shimanouchi T.Nishizawa H. J. Org. Chem. 1996, 61: 984 - 23
Chamchaang W.Pinhas AR. J. Org. Chem. 1990, 55: 2943
References
For an example of a rapid, zeolite-catalyzed aminolysis of a hindered epoxide, see ref. 6aa.