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DOI: 10.1055/s-2002-33635
Recent Developments in the Chemistry of Lithiated Epoxides
Publication History
Publication Date:
05 September 2002 (online)
![](https://www.thieme-connect.de/media/synthesis/200212/lookinside/thumbnails/10.1055-s-2002-33635-1.jpg)
Abstract
Although the lithium base-induced β-elimination of epoxides to allylic alcohols is a well-known reaction, α-lithiation has also been described many times. The resulting lithiated epoxides, first postulated as intermediates by Cope in 1951, have been invoked in a wide range of reactions, with their carbenoid properties allowing for very different reactivities. This review covers the recent advances (˜1996 - mid 2002) in the rich chemistry of these main-group metal carbenoids, especially their generation by enantioselective α-deprotonation.
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1 Introduction
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2 Carbenoid Chemistry of Lithiated Epoxides: C-H Insertion and 1,2-Shifts
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2.1 Transannular C-H Insertion
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2.2 Transannular Rearrangement versus 1,2-Shift of Hydrogen
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2.3 1,2-Shifts
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2.4 Cyclopropanations
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3 Carbenoid Chemitry of Lithiated Epoxides: Reductive Alkylation
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3.1 Olefin Formation: Allylic Alcohols via Reductive Alkylation
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3.2 Olefin Formation versus C-H Insertion
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3.3 Olefin Formation versus Electrophile Trapping
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4 Electrophile Trapping of Lithiated Epoxides
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4.1 Lithiated Epoxides Bearing Anion Stabilising Groups
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4.1.1 Transmetallation of Stabilised Lithiated Epoxides
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4.1.2 Sulfonyl-stabilised Lithiated Epoxides
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4.1.3 Carbonyl-stabilised Lithiated Epoxides
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4.1.4 Oxazolinyl-stabilised Lithiated Epoxides
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4.1.5 Imine-substituted Lithiated Epoxides
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4.1.6 Trifluoromethyl-substituted Lithiated Epoxides
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4.1.7 Silyl-stabilised Lithiated Epoxides in Synthesis
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4.1.8 Phenyl-stabilised Lithiated Epoxide
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4.2 ‘Remote’ Stabilisation of a Lithiated Epoxide
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4.3 Generation of Non-stabilised and Destabilised Lithiated Epoxides
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4.3.1 Desulfinylation of Sulfinyloxiranes
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4.3.2 Deprotonation of ‘Simple’ Epoxides
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5 Concluding Remarks
Key words
asymmetric synthesis - carbanions - carbenoids - epoxides - rearrangements
- 1
Satoh T. Chem. Rev. 1996, 96: 3303 - 2
Thurner A.Faigl F.Mordini A.Bigi A.Reginato G.Töke L. Tetrahedron 1998, 54: 11597 - 3
Thurner A.Faigl F.Töke L.Mordini A.Valacchi M.Reginato G.Czira G. Tetrahedron 2001, 57: 8173 - 4
Erden I. In Comprehensive Heterocyclic Chemistry II Vol. 1A:Katritzky AR.Rees CW.Scriven EFV. Pergamon; Oxford: 1996. p.97 - 5
Jacobsen EN. Acc. Chem. Res. 2000, 33: 421 - 6
Schaus SE.Brandes BD.Larrow JF.Tokunaga M.Hansen KB.Gould AE.Furrow ME.Jacobsen EN. J. Am. Chem. Soc. 2002, 124: 1307 - 7
Crandall JK.Apparu M. Org. React. 1983, 29: 345 - 8
Seebach D. Angew. Chem., Int. Ed. Engl. 1988, 27: 1624 - 9
Collum DB. Acc. Chem. Res. 1993, 26: 227 - 10
Hodgson DM.Gibbs AR.Lee GP. Tetrahedron 1996, 52: 14361 - 11
Hodgson DM.Gibbs AR.Drew MGB. J. Chem. Soc., Perkin Trans. 1 1999, 3579 - 12
Denmark SE.Barsanti PA.Wong KT.Stavenger RA. J. Org. Chem. 1998, 63: 2428 -
13a
Bertilsson SK.Södergren MJ.Andersson PG. J. Org. Chem. 2002, 67: 1567 -
13b
Magnus A.Bertilsson SK.Andersson PG. Chem. Soc. Rev. 2002, 31: 223 - 14
Cope AC.Tiffany BD. J. Am. Chem. Soc. 1951, 73: 4158 - 15
Morgan KM.Gajewski JJ. J. Org. Chem. 1996, 61: 820 - 16
Eisch JJ.Galle JE. J. Am. Chem. Soc. 1976, 98: 4646 - 17
Boche G.Lohrenz JCW. Chem. Rev. 2001, 101: 697 - 18
Morgan KM.Gronert S. J. Org. Chem. 2000, 65: 1461 - 19
Ramirez A.Collum DB. J. Am. Chem. Soc. 1999, 121: 11114 - 20
Cope AC.Trumbull PA.Trumbull ER. J. Am. Chem. Soc. 1958, 80: 2844 - 21
Cope AC.Lee H.-H.Petree HE. J. Am. Chem. Soc. 1958, 80: 2849 - 22
Hodgson DM.Lee GP.Marriott RE.Thompson AJ.Wisedale R.Witherington J. J. Chem. Soc., Perkin Trans. 1 1998, 2151 - 23
Boeckman RK., Jr. Tetrahedron Lett. 1977, 49: 4281 - 24
Hoppe D.Hense T. Angew. Chem., Int. Ed. Engl. 1997, 36: 2282 - 25
Hodgson DM.Lee GP. Chem. Commun. 1996, 1015 - 26
Beak PJ.Kerrick ST.Wu S.Chu J. J. Am. Chem. Soc. 1994, 116: 3231 - 27
Hodgson DM.Lee GP. Tetrahedron: Asymmetry 1997, 8: 2303 - 28
Gallagher DJ.Wu S.Nikolic NA.Beak PJ. J. Org. Chem. 1995, 60: 8148 - 29
Zschage O.Hoppe D. Tetrahedron 1992, 48: 5657 - 30
Kang J.Cho WO.Cho HG. Tetrahedron: Asymmetry 1994, 5: 1347 - 31
Kang J.Kim JI.Lee JH. Bull. Kor. Chem. Soc. 1994, 15: 865 - 32
Alexakis A.Vrancken E.Mangeney P. J. Chem. Soc., Perkin Trans. 1 2000, 3354 - 33
Alexakis A.Vrancken E.Mangeney P. Synlett 1998, 1165 - 34
Hodgson DM.Cameron ID. Org. Lett. 2001, 3: 441 - 35
Hodgson DM.Cameron ID.Christlieb M.Green R.Lee GP.Robinson LA. J. Chem. Soc., Perkin Trans. 1 2001, 2161 - 36
Hodgson DM.Robinson LA. Chem. Commun. 1999, 309 - 37
Hodgson DM.Wisedale R. Tetrahedron: Asymmetry 1996, 7: 1275 - 38
Hodgson DM.Maxwell CR.Matthews IR. Tetrahedron: Asymmetry 1999, 10: 1847 - 39
Hodgson DM.Maxwell CR.Matthews IR. Synlett 1998, 1349 - 40
Hodgson DM.Maxwell CR.Wisedale R.Matthews IR.Carpenter KJ.Dickenson AH.Wonnacott S. J. Chem. Soc., Perkin Trans. 1 2001, 3150 - 41
Hodgson DM.Marriott RE. Tetrahedron Lett. 1997, 38: 887 - 42
Hodgson DM.Marriott RE. Tetrahedron: Asymmetry 1997, 8: 519 - 43
Thies RW.Chiarello RH. J. Org. Chem. 1979, 44: 1342 - 44
Yanagisawa A.Yasue K.Yamamoto H. J. Chem. Soc., Chem. Commun. 1994, 2103 - 45
Hodgson DM.Robinson LA.Jones ML. Tetrahedron Lett. 1999, 40: 8637 - 46
Doris E.Dechoux L.Mioskowski C. J. Am. Chem. Soc. 1995, 117: 12700 - 47
Doris E.Mioskowski C.Dechoux L.Agami C. J. Org. Chem. 1998, 63: 3808 - 48
Morgan KM.O’Connor MJ.Humphrey JL.Buschman KE. J. Org. Chem. 2001, 66: 1600 - 49
Agami C.Dechoux L.Doris E.Mioskowski C. Tetrahedron Lett. 1997, 38: 4071 - 50
Dechoux L.Agami C.Doris E.Mioskowski C. Eur. J. Org. Chem. 2001, 4107 - 51
Crandall JK.Lin L.-HC. J. Am. Chem. Soc. 1967, 89: 4526 - 52
Crandall JK.Lin L.-HC. J. Am. Chem. Soc. 1967, 89: 4527 - 53
Doris E.Dechoux L.Mioskowski C. Tetrahedron Lett. 1994, 35: 7943 - 54
Doris E.Dechoux L.Mioskowski C. Synlett 1998, 337 - 55
Dechoux L.Doris E.Mioskowski C. Chem. Commun. 1996, 549 - 56
Hodgson DM.Stent MAH.Wilson FX. Org. Lett. 2001, 3: 3401 - 57
Hodgson DM.Stent MAH.Wilson FX. Synthesis 2002, 1445 - 58
Hodgson DM.Miles TJ.Witherington J. Synlett 2002, 310 - 59
Dechoux L.Agami C.Doris E.Mioskowski C. J. Org. Chem. 1999, 64: 9279 - 60
Shimizu M.Fujimoto T.Minezaki H.Hata T.Hiyama T. J. Am. Chem. Soc. 2001, 123: 6947 - 61
Kasatkin AN.Whitby RJ. Tetrahedron Lett. 2000, 41: 5275 - 62
Kasatkin AN.Whitby RJ. Tetrahedron Lett. 2000, 41: 6201 - 63
Ashwell M.Jackson RFW. J. Chem. Soc., Chem. Commun. 1988, 645 - 64
Ashwell M.Jackson RFW. J. Chem. Soc., Perkin Trans. 1 1989, 835 - 65
Hewkin CT.Jackson RFW.Clegg W. J. Chem. Soc., Perkin Trans. 1 1991, 3091 - 66
Hewkin CT.Jackson RFW. J. Chem. Soc., Perkin Trans. 1 1991, 3103 - 67
Jackson RFW.Standen SP.Clegg W. Tetrahedron Lett. 1991, 32: 5393 - 68
Ashwell M.Clegg W.Jackson RFW. J. Chem. Soc., Perkin Trans. 1 1991, 897 - 69
Dunn SFC.Jackson RFW. J. Chem. Soc., Perkin Trans. 1 1992, 2863 - 70
Mori Y.Yaegashi K.Iwase K.Yamamori Y.Furukawa H. Tetrahedron Lett. 1996, 37: 2605 - 71
Mori Y.Yaegashi K.Kwase K.Yamamori Y.Furukawa H. Tetrahedron Lett. 1996, 37: 6959 - 72
Mori Y.Yaegashi K.Furukawa H. Tetrahedron Lett. 1999, 40: 7239 - 73
Mori Y.Furuta H.Takase T.Mitsuoka S.Furukawa H. Tetrahedron Lett. 1999, 40: 8019 - 74
Mori Y.Yaegashi K.Furukawa H. J. Am. Chem. Soc. 1996, 118: 8158 - 75
Mori Y. Chem.-Eur. J. 1997, 3: 849 - 76
Mori Y.Sawada T.Furukawa H. Tetrahedron Lett. 1999, 40: 731 - 77
Mori Y.Yaegashi K.Furukawa H. J. Am. Chem. Soc. 1997, 119: 4557 - 78
Mori Y.Yaegashi K.Furukawa H. Tetrahedron 1997, 53: 12917 - 79
Mori Y.Yaegashi K.Furukawa H. J. Org. Chem. 1998, 63: 6200 - 80
Mori Y. Rev. Heteroat. Chem. 1997, 17: 183 - 81
Kuramochi K.Itaya H.Nagata S.Takao K.-I.Kobayashi S. Tetrahedron Lett. 1999, 40: 7367 - 82
Kuramochi K.Nagata S.Itaya H.Takao K.-I.Kobayashi S. Tetrahedron Lett. 1999, 40: 7371 - 83
Florio S.Ingrosso G.Troisi L.Lucchini V. Tetrahedron Lett. 1993, 34: 1363 - 84
Florio S.Capriati V.Di Martino S. Tetrahedron Lett. 1998, 39: 5639 - 85
Florio S.Capriati V.Di Martino S.Abbotto A. Eur. J. Org. Chem. 1999, 409 - 86
Abbotto A.Capriati V.Degennaro L.Florio S.Luisi R.Pierrot M.Salomone A. J. Org. Chem. 2001, 66: 3049 - 87
Capriati V.Florio S.Luisi R.Russo V.Salomone A. Tetrahedron Lett. 2000, 41: 8835 - 88
Capriati V.Degennaro L.Favia R.Florio S.Luisi R. Org. Lett. 2002, 4: 1551 - 89
Alickmann D.Fröhlich R.Würthwein E.-U. Org. Lett. 2001, 3: 1527 - 90
Yamauchi Y.Katagiri T.Uneyama K. Org. Lett. 2002, 4: 173 - 91
Mani NS.Townsend CA. J. Org. Chem. 1997, 62: 636 - 92
Marié J.-C.Courillon C.Malacria M. Synlett 2002, 553 - 93
Witherington J. PhD Thesis University of Reading; UK: 1994. - 94
Capriati V.Florio S.Luisi R.Salomone A. Org. Lett. 2002, 4: 2445 - 95
Lertvorachon J.Thebtaranonth Y.Thongpanchang T.Thongyoo P. J. Org. Chem. 2001, 66: 4692 - 96
Satoh T.Kaneko Y.Yamakawa K. Bull. Chem. Soc. Jpn. 1986, 59: 2463 - 97
Satoh T.Kaneko Y.Yamakawa K. Tetrahedron Lett. 1986, 27: 2379 - 98
Satoh T.Itoh M.Yamakawa K. Chem. Lett. 1987, 1949 - 99
Satoh T.Oohara T.Ueda Y.Yamakawa K. Tetrahedron Lett. 1988, 29: 313 - 100
Satoh T.Oohara T.Yamakawa K. Tetrahedron Lett. 1988, 29: 2851 - 101
Satoh T.Oohara T.Ueda Y.Yamakawa K. J. Org. Chem. 1989, 54: 3130 - 102
Satoh T.Horigushi K. Tetrahedron Lett. 1995, 36: 8235 - 103
Satoh T.Kobayashi S.Nakanishi S.Horigushi K.Irisa S. Tetrahedron 1999, 55: 2515 - 104
Hodgson DM.Norsikian SLM. Org. Lett. 2001, 3: 461 - 105
Hodgson DM.Gras E. Angew. Chem. Int. Ed. 2002, 41: 2376 - 106
Johnson RA.Sharpless KB. In Catalytic Asymmetric Synthesis 2nd Ed.:Ojima I. Wiley-VCH; New York: 2000. p.231 - 107
Jacobsen EN.Wu MH. In Comprehensive Asymmetric CatalysisJacobsen EN.Pfaltz A.Yamamoto H. Springer-Verlag; Berlin: 1999. p.649 - 108
Aggarwal VK.Alonso E.Hynd G.Lydon KM.Palmer MJ.Porcelloni M.Studley JR. Angew. Chem. Int. Ed. 2001, 40: 1430