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Volumn 48, Issue 9, 2009, Pages 1644-1647

A palladium(II)-catalyzed synthesis of spiroacetals through a one-pot multicomponent cascade reaction

Author keywords

Cyclization; Homogeneous catalysis; Multicomponent reactions; Palladium; Spiroacetals

Indexed keywords

AMINES; CATALYSIS; CYCLIZATION; OXYGEN; PALLADIUM; REACTION KINETICS; SYNTHESIS (CHEMICAL);

EID: 60749097519     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200805519     Document Type: Article
Times cited : (97)

References (59)
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    • also see: b) L.-G. Milroy, G. Zinzalla, G. Prencipe, P. Michel, S. V. Ley, M. Gunaratnam, M. Beltran, S. Neidle, Angew. Chem. 2007, 119, 2545-2548;
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    • The stereostructure of berkelic acid has been recently revised: b P. Buchgraber, T. N. Snaddon, C. Wirtz, R. Mynott, R. Goddard, A. Fürstner, Angew. Chem. 2008, 120, 8578-8582;
    • The stereostructure of berkelic acid has been recently revised: b) P. Buchgraber, T. N. Snaddon, C. Wirtz, R. Mynott, R. Goddard, A. Fürstner, Angew. Chem. 2008, 120, 8578-8582;
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    • For related spiroacetal epimerization processess, see: a
    • For related spiroacetal epimerization processess, see: a) M. J. Gaunt, D. F. Hook, H. R. Tanner, S. V. Ley, Org. Lett. 2003, 5, 4815-4818;
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    • The isomers diast-4 seem to be the kinetically preferred compounds as we observed that at low conversion (ca. 10%) the ratio of diast-4/4 is approximately 2:1. After complete conversion the ratio became 1:1 and no change in this ratio was observed by stirring the reaction for a longer time (4 days). These results seem to indicate that the palladium species can not effect the complete isomerization of diast-4 into 4 in a reasonable time, even at higher palladium loadings (10 mol%).
    • The isomers diast-4 seem to be the kinetically preferred compounds as we observed that at low conversion (ca. 10%) the ratio of diast-4/4 is approximately 2:1. After complete conversion the ratio became 1:1 and no change in this ratio was observed by stirring the reaction for a longer time (4 days). These results seem to indicate that the palladium species can not effect the complete isomerization of diast-4 into 4 in a reasonable time, even at higher palladium loadings (10 mol%).
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    • CCDC 707907 (4d), 707906 (12 c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
    • CCDC 707907 (4d), 707906 (12 c) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
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    • The palladium(II)-catalyzed cycloisomerization of alkynol derivatives to give enol ethers or related compounds is a well established reaction. For references, see: A) K. Utimoto
    • The palladium(II)-catalyzed cycloisomerization of alkynol derivatives to give enol ethers or related compounds is a well established reaction. For references, see: a) K. Utimoto, Pure Appl. Chem. 1983, 55, 1845-1852;
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    • The palladium(II) complex may act as a Lewis acid catalyst that activates the imine. For an excellent account on σ- and π-electrophilic Lewis acids, see: A) Y. Yamamoto
    • The palladium(II) complex may act as a Lewis acid catalyst that activates the imine. For an excellent account on σ- and π-electrophilic Lewis acids, see: a) Y. Yamamoto, J. Org. Chem. 2007, 72, 7817-7831.
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    • Alternatively, the formation of an o-quinonemethide intermediate from the imine 6 could also be considered, see: b R. S. Kumar, R. Nagarajan, P. T. Perumal, Synthesis 2004, 949-959.
    • Alternatively, the formation of an o-quinonemethide intermediate from the imine 6 could also be considered, see: b) R. S. Kumar, R. Nagarajan, P. T. Perumal, Synthesis 2004, 949-959.
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    • The structural assignment of the chiral compounds 12g-i is based on extensive NMR spectroscopy investigations and is in agreement with the excellent work recently published by Fürstner and co-workers, see reference [7b]. Interestingly, the relative stereostructure of compounds 12g-i is the same as that found by these authors in the related revised structure of berkelic acid.
    • The structural assignment of the chiral compounds 12g-i is based on extensive NMR spectroscopy investigations and is in agreement with the excellent work recently published by Fürstner and co-workers, see reference [7b]. Interestingly, the relative stereostructure of compounds 12g-i is the same as that found by these authors in the related revised structure of berkelic acid.
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    • The acetal intermediate may evolve by formation of an o-quinonemethide intermediate, see reference [14].
    • The acetal intermediate may evolve by formation of an o-quinonemethide intermediate, see reference [14].
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    • For recently reported related strategies to synthesize chroman spiroacetals, see: a
    • For recently reported related strategies to synthesize chroman spiroacetals, see: a) G. Zhou, J. Zhu, Z. Xie, Y. Li, Org. Lett. 2008, 10, 721-724;
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    • Zhou, G.1    Zhu, J.2    Xie, Z.3    Li, Y.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.