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DOI: 10.1055/s-2005-865214
Chiral-Auxiliary-Controlled Diastereoselective Epoxidations
Publication History
Publication Date:
14 April 2005 (online)
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Abstract
An overview of the literature through May 2004 on the available chiral auxiliaries for stereoselective epoxidation is reviewed, with emphasis on synthetic utility. The mechanistic complexities of the π-facial selectivity are scrutinized and plausible transition structures for the oxygen-transfer process are proposed. Convenient methods for the removal of the chiral auxiliary and applications of the released optically active building blocks in synthesis are featured.
1 Introduction
2 Types of Chiral Auxiliaries
2.1 Amides
2.2 Oxazolidines
2.3 Enecarbamates
2.4 Esters
2.5 Acetals
2.6 Enol Ethers
3 Removal of the Chiral Auxiliary
4 Chiral-Auxiliary-Mediated Epoxidations in Synthesis
5 Outlook
Key words
alkenes - mechanisms - oxidations - oxygen transfer - stereoselectivity - synthesis
-
1a
Carey FA.Sundberg RJ. Advanced Organic Chemistry 3rd ed.: Plenum Press; New York: 1990. p.624 -
1b
Fringuelli F.Piermatti O.Pizzo F. Trends Org. Chem. 1997, 6: 181 -
1c
Chemla F.Ferreira F. Curr. Org. Chem. 2002, 6: 539 -
2a
Rao AS.Paknokov SK.Kirtane JG. Tetrahedron 1983, 39: 2323 -
2b
Smith JG. Synthesis 1984, 629 - 3
Paterson I.Berrisford DJ. Angew. Chem., Int. Ed. Engl. 1992, 31: 1179 -
4a
Hodgson DM.Gibbs AR.Lee GP. Tetrahedron 1996, 52: 14361 -
4b
Jacobsen EN. Acc. Chem. Res. 2000, 33: 421 - 5
Erden I. In Comprehensive Heterocyclic Chemistry II Vol. 1A:Katritzky AR.Rees CW.Scriven EFV. Elsevier; Oxford: 1996. p.105 - 6
Jacobsen EN. In Comprehensive Organometallic Chemistry II Vol. 12:Wilkinson G.Stone FGA.Abel EW.Hegedus LS. Pergamon; New York: 1995. Chap. 11.1. -
7a
Jesberger M.Davis TP.Barner L. Synthesis 2003, 1929 -
7b
Adam W.Bargon RM. Chem. Rev. 2004, 104: 251 -
8a
Katsuki T. In Catalytic Asymmetric SynthesisOjima I. Wiley-VCH; Weinheim: 2000. p.287 -
8b
Jacobsen EN.Wu MH. In Comprehensive Asymmetric CatalysisJacobsen EN.Pfaltz A.Yamamoto H. Springer; Berlin: 1999. p.649 - 9
Hoveyda AH.Evans DA.Fu GC. Chem. Rev. 1993, 93: 1307 - 10
Johnson RA.Sharpless KB. In Catalytic Asymmetric SynthesisOjima I. VCH; New York: 1993. p.103 - 11
Jacobsen EN. In Catalytic Asymmetric SynthesisOjima I. VCH; New York: 1993. p.159 - 12
Katsuki T. Coord. Chem. Rev. 1995, 140: 189 - 13
Adam W.Malisch W.Roschmann KJ.Saha-Möller CR.Schenk WA. J. Organomet. Chem. 2002, 661: 3 - 14
Wu XY.She XG.Shi Y. J. Am. Chem. Soc. 2002, 124: 8792 -
15a
Collman JP.Wang Z.Straumanis A.Quelquejeu M.Rose E. J. Am. Chem. Soc. 1999, 121: 460 -
15b
Collmann JP.Zhang X.Lee VJ.Uffelman ES.Brauman JI. Science 1993, 261: 1404 - 16
Zhang R.Yu WY.Sun HZ.Liu WS.Che CM. Chem.-Eur. J. 2002, 8: 2495 -
17a
Inanaga J.Furuno H.Hayano T. Chem. Rev. 2002, 102: 2211 -
17b
Sharpless KB. Angew. Chem. Int. Ed. 2002, 41: 2024 -
17c
Bonini C.Righi G. Tetrahedron 2002, 58: 4981 -
17d
Lane BS.Burgess K. Chem. Rev. 2003, 103: 2457 -
18a
Adam W.Saha-Möller CR.Ganeshpure P. Chem. Rev. 2001, 101: 3499 -
18b
Frohn M.Shi Y. Synthesis 2000, 1979 -
18c
Adam W.Zhao C.-G.Saha-Möller CR. Org. React. 2002, 61: 219 -
19a
Jones S. J. Chem. Soc., Perkin Trans. 1 2002, 1 -
19b
O’Brien P. J. Chem. Soc., Perkin Trans. 1 2001, 95 -
19c
Regan AC. J. Chem. Soc., Perkin Trans. 1 1999, 357 - 20
Bach RD.Dmitrenko O. J. Phys. Chem. A 2003, 107: 4300 -
21a
Kunz H.Rück K. Angew. Chem., Int. Ed. Engl. 1993, 32: 336 -
21b
Vega-Pérez JM.Vega M.Blanco E.Iglesias-Guerra F. Tetrahedron: Asymmetry 2001, 12: 3189 - 22
Adam W.Pastor A.Peters K.Peters EM. Org. Lett. 2000, 2: 1019 - 23
Adam W.Smerz AK. Bull. Soc. Chim. Belg. 1996, 105: 581 - 24
Taft RW.Kamlet MJ. J. Am. Chem. Soc. 1976, 98: 2886 -
25a
Kanemasa S.Onimura K. Tetrahedron 1992, 48: 8631 -
25b
Porter NA.Rosenstein IJ.Breyer RA.Bruhnke JD.Wu W.-X.McPhail AT. J. Am. Chem. Soc. 1992, 114: 7664 -
26a
Oppolzer W.Mills RJ.Réglier M. Tetrahedron Lett. 1986, 27: 183 -
26b
Curran DP.Heffner TA. J. Org. Chem. 1990, 55: 4585 - 27
Kim BH.Curran DP. Tetrahedron 1993, 49: 293 - 28
Dewar MJS.Zoebisch EG.Healy EF.Stewart JP. J. Am. Chem. Soc. 1985, 107: 3902 - 29
Nandy JP.Prabhakaran EN.Kiran Kumar S.Kunmar AC.Iqbal J. J. Org. Chem. 2003, 68: 1679 - 30
Adam W.Zhang AM. Eur. J. Org. Chem. 2004, 147 - 31
Baumstark AL.Vasquez PC. J. Org. Chem. 1988, 53: 3437 - 32
Fan CL.Lee WD.Teng NW.Sun YC.Chen K. J. Org. Chem. 2003, 68: 9816 - 33
Fan CL.Reddy GS.Chen K. J. Chin. Chem. Soc. 2003, 50: 1047 -
34a
Adam W.Brunker H.-G.Kumar AS.Peters E.-M.Peters K.Schneider U.von Schnering HG. J. Am. Chem. Soc. 1996, 118: 1899 -
34b
Kocovsky P.Stary I. J. Org. Chem. 1990, 55: 3236 - 35
Jenson C.Liu J.Houk KN.Jorgensen WL. J. Am. Chem. Soc. 1997, 119: 12982 - 36
Meth-Cohn O.Chen Y. Tetrahedron Lett. 1999, 40: 6069 - 37
Meth-Cohn O.Williams DJ.Chen Y. Chem. Commun. 2000, 495 - 38
Adam W.Schambony SB. Org. Lett. 2001, 3: 79 - 39
Adam W.Peters K.Peters E.-M.Schambony SB. J. Am. Chem. Soc. 2001, 123: 7228 - 40
Cardani S.Gennari C.Scolastico C.Villa R. Tetrahedron 1989, 45: 7397 - 41
Evans DA.Chapman KT.Bisaha J. J. Am. Chem. Soc. 1988, 110: 1238 - 42
Xiong H.Hsung RP.Shen L.Hahn JM. Tetrahedron Lett. 2002, 43: 4449 - 43
Adam W.Bosio SG.Wolff BT. Org. Lett. 2003, 5: 819 - 44
Adam W.Bosio SG.Turro NJ. J. Am. Chem. Soc. 2002, 124: 8814 - 45
Adam W.Bosio SG.Turro NJ.Wolff BT. J. Org. Chem. 2004, 69: 1704 -
46a
Rameshkumar C.Xiong H.Tracey MR.Berry CR.Yao LJ.Hsung RP. J. Org. Chem. 2002, 67: 1339 -
46b
Pusion A.Rosnati V.Solinas C. Tetrahedron 1983, 39: 2259 - 47
Xiong H.Hsung RP.Berry CR.Rameshkumar C. J. Am. Chem. Soc. 2001, 123: 7174 - 48
Taylor DAH.Wragg K. J. Chem. Soc., Chem. Commun. 1967, 81 - 49
Ohno N.Mabry TJ. Phytochemistry 1979, 18: 1003 - 50
Bohlmann F.Zdero C. Liebigs Ann. Chem. 1985, 1764 - 51
Torres-Valencia JM.Cerda-Garcia-Rojas CM.Joseph-Nathan P. Tetrahedron: Asymmetry 1995, 6: 1611 - 52
Torres-Valencia JM.Cerda-Garcia-Rojas CM.Joseph-Nathan P. Tetrahedron: Asymmetry 1998, 9: 757 - 53
Meth-Cohn O.Moore C.Taljaard HC. J. Chem. Soc., Perkin Trans. 1 1988, 2663 - 54
Clark C.Hermans P.Meth-Cohn O.Moore C.Taljaard HC.Vuuren GV. J. Chem. Soc., Chem. Commun. 1986, 1378 - 55
Porter MJ.Skidmore J. Chem. Commun. 2000, 1215 - 56
Meth-Cohn O. J. Chem. Soc., Chem. Commun. 1986, 695 - 57
Bellucci G.Catelani G.Chiappe C.D’Andrea F.Grigò G. Tetrahedron: Asymmetry 1997, 8: 765 - 58
Charette AB.Côté B. Tetrahedron: Asymmetry 1993, 4: 2283 - 59
Vega-Pérez JM.Candela JI.Romero I.Blanco E.Iglesias-Guerra F. Eur. J. Org. Chem. 2000, 3949 - 60
Vega-Pérez JM.Candela JI.Blanco E.Iglesias-Guerra F. Tetrahedron: Asymmetry 2002, 13: 2471 - 61
Harada T.Nakajima H.Ohnishi T.Takeuchi M.Oku A. J. Org. Chem. 1992, 57: 720 - 62
White JD.Theramongkol P.Kuroda C.Engebrecht JR. J. Org. Chem. 1988, 53: 5909 - 63
Sugimura T.Futagawa T.Tai A. Tetrahedron Lett. 1988, 29: 5775 - 64
Sugimura T.Yoshikawa M.Futagawa T.Tai A. Tetrahedron 1990, 46: 5955 - 65
Sugimura T.Nishiyama N.Tai A.Hakushi T. Tetrahedron: Asymmetry 1993, 4: 43 - 66
Underiner TL.Paquette LA. J. Org. Chem. 1992, 57: 5348 - 67
Bhatia GS.Lowe RF.Pritchard RG.Stoodley RJ. Chem. Commun. 1997, 1981 - 68
Bhatia GS.Lowe RF.Stoodley RJ. Tetrahedron Lett. 1998, 39: 9245 - 69
Seebach D.Naef R.Calderari G. Tetrahedron 1984, 40: 1313 - 70
Sharpless KB.Amberg W.Bennani YL.Crispino GA.Hartung J.Joeng KS.Kwong HL.Morika AK.Wang ZM.Xu DQ.Zhang XL. J. Org. Chem. 1992, 57: 2768 - 71
Davies SG.Key MS.Rodriguez-Solla H.Sanganee HJ.Savory ED.Smith AD. Synlett 2003, 1659 - 72
Dung JS.Armstrong RW.Anderson OP.Williams RM. J. Org. Chem. 1983, 48: 3592 - 73
Yamada T.Suzuki H.Mukaiyama T. Chem. Lett. 1987, 2: 293