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Volumn 48, Issue 42, 2009, Pages 7899-7903

Et2SBr.SbCl5Br: An effective reagent for direct bromonium-induced polyene cyclizations

Author keywords

Biomimetic synthesis; Bromine; Isocymobarbatol; Polyene cyclization; Terpene

Indexed keywords

BIOMIMETIC SYNTHESIS; CYCLIZATIONS; FARNESOL; GOOD YIELD; ISOCYMOBARBATOL; LABORATORY METHODS; POLYENE CYCLIZATION; SIX-MEMBERED RINGS; TERPENE;

EID: 70349668795     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200903834     Document Type: Article
Times cited : (141)

References (60)
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    • A graphical summary of all of the bromonium-induced cyclizations in Refs. [6-8] can. be found at the end of the Supporting Information to provide a full sense of the true stateof-the-art in these reactions in racemic format
    • A. Tanaka, T. Oritani, Biosci. Biotechnol. Biochem. 1995, 59, 516-517. A graphical summary of all of the bromonium-induced cyclizations in Refs. [6-8] can. be found at the end of the Supporting Information to provide a full sense of the true stateof-the-art in these reactions in racemic format.
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    • It should be noted that this paper describes asymmetric iodoniuminduced cyclizations of three structurally similar geraniolderived substrates possessing electron-rich alkene nucleophiles; attempts to extend the developed system directly to bromine afforded products in poor enantiomeric excess, revealing that the problem of inducing asymmetry in this transformation is far from a trivial one; these challenges, of course, are in addition to those described for effecting bromonium-induced cyclizations in racemic format as already described
    • A. Sakakura, A. Ukai, K. Ishihara, Nature 2007, 445, 900-903. It should be noted that this paper describes asymmetric iodoniuminduced cyclizations of three structurally similar geraniolderived substrates possessing electron-rich alkene nucleophiles; attempts to extend the developed system directly to bromine afforded products in poor enantiomeric excess, revealing that the problem of inducing asymmetry in this transformation is far from a trivial one; these challenges, of course, are in addition to those described for effecting bromonium-induced cyclizations in racemic format as already described.
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    • Related reagents with different Lewis acidic counterions have been known for far longer, though again, their reactivity with olefins or other nucleophilies remains unreported
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    • 2S leads to competent reagents for cation-π cyclization; however, 13 is the most easily prepared and crystallized. We propose giving compound 13 the acronym of BDSB for bromodiethylsulfonium bromopentachloroantimonate
    • 2S leads to competent reagents for cation-π cyclization; however, 13 is the most easily prepared and crystallized. We propose giving compound 13 the acronym of BDSB for bromodiethylsulfonium bromopentachloroantimonate.
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    • 2, 1,2dichloroethane, chloroform, and toluene, and insoluble in benzene, hexanes, and pentane. We have observed that 13 is soluble in. acetone, methanol, ethanol, and THF, but reacts with these solvents
    • 2, 1,2dichloroethane, chloroform, and toluene, and insoluble in benzene, hexanes, and pentane. We have observed that 13 is soluble in. acetone, methanol, ethanol, and THF, but reacts with these solvents.
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    • For the synthesis of these substrates, see the Supporting Information
    • For the synthesis of these substrates, see the Supporting Information.
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    • Although not reported to initiate cation-π cyclizations, bis(collidine)halonium triflate and Perchlorate salts have been utilized as sources of electrophilic halogen. For selected examples
    • Although not reported to initiate cation-π cyclizations, bis(collidine)halonium triflate and Perchlorate salts have been utilized as sources of electrophilic halogen. For selected examples, see: a) R. U. Lemieux, A. R. Morgan, Can. J. Chem. 1965, 43, 2190-2197;
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    • 2/ AgBF4 and entry 1 for TBCO. Each of these precedents is fully elucidated in the Supporting Information
    • 2/ AgBF4 and entry 1 for TBCO. Each of these precedents is fully elucidated in the Supporting Information.
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    • 3P under the utilized conditions in 71 % yield; we have been, unable to achieve similar results despite several attempts. Rather than, offer any questioning of this precedent, we would argue instead here that our protocol provides for easier execution since temperature control over the course of 30 h is not required
    • 3P under the utilized conditions in 71 % yield; we have been, unable to achieve similar results despite several attempts. Rather than, offer any questioning of this precedent, we would argue instead here that our protocol provides for easier execution since temperature control over the course of 30 h is not required.
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    • ' adducts generated
    • ' adducts generated.
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    • In all cases, the stereochemistry of products was confirmed by NMR analysis as well as comparison to published characterization data. In particular, at least in terms of NMR analyses, any alteration in. the axial or equatorial disposition, of groups attached to the carbocycle are highly diagnostic signals. To verify the nerol cyclization case, we obtained a crystal structure for 36 (a picture of which is shown in the Supporting Information) since precedent for cyclizations with these substrates is sparse
    • In all cases, the stereochemistry of products was confirmed by NMR analysis as well as comparison to published characterization data. In particular, at least in terms of NMR analyses, any alteration in. the axial or equatorial disposition, of groups attached to the carbocycle are highly diagnostic signals. To verify the nerol cyclization case, we obtained a crystal structure for 36 (a picture of which is shown in the Supporting Information) since precedent for cyclizations with these substrates is sparse.
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    • 4 (cf. Ref. [7a])
    • 4 (cf. Ref. [7a]).
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    • 3 to the reaction media prior to BDSB addition. It could also be suppressed by adding a cold solution of BDSB very quickly to the substrate
    • 3 to the reaction media prior to BDSB addition. It could also be suppressed by adding a cold solution of BDSB very quickly to the substrate.
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    • Conceptually, the reagent described herein can be defined as Lewis base activation of a Lewis acid. For a review on this important mode of promoting reactivity from, one of its leading practitioners
    • Conceptually, the reagent described herein can be defined as Lewis base activation of a Lewis acid. For a review on this important mode of promoting reactivity from, one of its leading practitioners, see : S. E. Denmark, G. L. Beutner, Angew. Chem. 2008, 120, 1584-1663;
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    • Denmark, S.E.1    Beutner, G.L.2
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    • For a recent paper on the use of this approach to attempt enantioselective addition of chalcogens such as sulfur onto alkenes
    • For a recent paper on the use of this approach to attempt enantioselective addition of chalcogens such as sulfur onto alkenes, see: S. E. Denmark, W. R. Collins, M. D. Cullin, J. Am. Chem. Soc. 2009, 131, 3490-3492.
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    • The crystal structure of 1.3 is noted as preliminary since disorder resulting from, halide exchanges between the halogen atoms attached to the antimony counterion prevents a consistent unit cell
    • The crystal structure of 1.3 is noted as preliminary since disorder resulting from, halide exchanges between the halogen atoms attached to the antimony counterion prevents a consistent unit cell.
  • 59


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