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DOI: 10.1055/s-2004-825593
Asymmetric Iodocyclization of γ-Hydroxyalkenes
Publikationsverlauf
Publikationsdatum:
10. Mai 2004 (online)
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Abstract
Enantioselective intramolecular iodoetherification of disubstituted γ-hydroxyalkenes has been intended using NIS in the presence of 0.2 equivalents of (R)-Binol-Ti(IV) complex to procure the corresponding tetrahydrofurans in up to 65% ee.
Key words
reagent-controlled - iodocyclization - γ-hydroxyalkenes - (R)-Binol-Ti(IV) complex - N-iodosuccinimide
-
1a
Rousseau G.Robin S. Tetrahedron 1998, 54: 13681 -
1b
Harding KE.Tinger TH. In Comprehensive Organic Synthesis Vol. 4:Trost BM.Fleming I. Pergamon; Oxford: 1991. p.463 -
1c
Mulzer J. In Organic Synthesis Highlights VCH; Weinheim: 1991. p.157 -
2a
Fuji K.Node M.Naniwa Y.Kawabata T. Tetrahedron Lett. 1990, 31: 3175 -
2b
Furth M.Brown EG. J. Am. Chem. Soc. 1987, 109: 6844 -
3a
Back TG.Dyck BP.Nan S. Tetrahedron 1999, 55: 3191 -
3b
Nishibayashi Y.Srivastava SK.Takada H.Fukuzawa S.-I.Uemura S. J. Chem. Soc., Chem. Commun. 1995, 2321 -
3c
Wirth T. Angew. Chem., Int. Ed. Engl. 1995, 34: 1726 -
3d
Fujita K.-I.Iwaoka M.Tomoda S. Chem. Lett. 1992, 1123 - 4
Kang SH.Kim M. J. Am. Chem. Soc. 2003, 125: 4684 -
5a
Hass J.Piguel S.Wirth T. Org. Lett. 2002, 4: 297 -
5b
Grossman RB.Trupp RJ. Can. J. Chem. 1998, 76: 1233 -
6a
Grundon MF.Stewart D.Watts WE. J. Chem. Soc., Chem. Commun. 1973, 573 -
6b
Carlson RM.Funk AH. Tetrahedron Lett. 1971, 27: 3661 - 7
Kang SH.Lee SB.Park CM. J. Am. Chem. Soc. 2003, 51: 15748 -
8a
Mikami K.Terada M.Matsumoto Y.Tanaka M.Nakamura Y. Micropor. Mesopor. Mater. 1998, 21: 461 -
8b
Terada M.Matsumoto Y.Nakamura Y.Mikami K. J. Mol. Catal. A: Chem. 1998, 132: 165 -
8c
Inoue T.Kitagawa O.Saito A.Taguchi T. J. Org. Chem. 1997, 62: 7384 -
8d
Keck GE.Krishnamurthy D. J. Am. Chem. Soc. 1995, 117: 2363 -
8e
Keck GE.Tarbet KH.Geraci LS. J. Am. Chem. Soc. 1993, 115: 8467 -
9a
Lingenfelter DS.Helgeson RC.Cram DJ. J. Org. Chem. 1981, 46: 393 -
9b
Hu Q.Vitharana D.Pu L. Tetrahedron: Asymmetry 1995, 6: 2123 -
9c
Qian C.Huang T.Zhu C.Sun J. J. Chem. Soc., Perkin Trans. 1 1998, 2097 -
9d
Cram DJ.Helgeson RC.Peacook SC.Kaplan LJ.Domeier LA.Moreau P.Koga K.Mayer JM.Chao Y.Siegel MG.Hoffmann DH.Sogah GDY. J. Org. Chem. 1978, 43: 1930
References
General Procedure for the Asymmetric Iodocyclization. To a mixture of (R)-Binol (17 mg, 0.06 mmol) and 4Å molecular sieve (57 mg) in t-butyl methyl ether (3.5 mL) was added Ti(Oi-Pr)4 (17 mg, 0.06 mmol) in t-butyl methyl ether (0.7 mL) at r.t., and the resulting mixture was stirred at that temperature for 1.5 h. After cooling the generated (R)-Binol-Ti(IV) complex to 0 °C, the substrate 2 (57 mg, 0.3 mmol) in t-butyl methyl ether (1.5 mL) and N-iodo-succinimide (81 mg, 0.36 mmol) were added in sequence. The iodocyclization was allowed to proceed at 0 °C for 3 h, and then quenched with 10% aq Na2S2O3 (3 mL). The reaction mixture was extracted with Et2O (3 × 5 mL), and subsequently the organic layer was filtered through celite. Evaporation of the volatile materials in vacuo followed by silica gel column chromatography (Et2O-hexane = 1:15) yielded tetrahydrofuran 3 (89 mg, 93%).