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Volumn 69, Issue 13, 2004, Pages 4412-4428

Lewis acid catalyzed allylboration: Discovery, optimization, and application to the formation of stereogenic quaternary carbon centers

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; ALDEHYDES; CATALYSIS; REACTION KINETICS; STEREOCHEMISTRY;

EID: 3042739843     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049773m     Document Type: Article
Times cited : (84)

References (122)
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    • For a recent review on the activation of allylsilanes and allylboronates, see: Kennedy, J. W. J.; Hall, D. G. Angew. Chem., Int. Ed. 2003, 42, 4732-4739.
    • (2003) Angew. Chem., Int. Ed. , vol.42 , pp. 4732-4739
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    • For a discussion of the different types of allylating reagents, see: (a) Denmark, S. E.; Weber, E. J. Helv. Chim. Acta 1983, 66, 1655-1660.
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    • note
    • See the Supporting Information for further details.
  • 52
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    • Of the numerous preparations of iodomethaneboronate 5a available, the one that we found to be the most convenient on large scale was: Phillion, D. P.; Neubauer, R.; Andrew, S. S. J. Org. Chem. 1986, 51, 1610-1612. For alternative preparations, see refs 44 and 23.
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    • note
    • 1H NOE experiments on the diastereomeric lactones 2i and 2j as well as by X-ray crystallography of lactone 2n. See the Supporting Information for details.
  • 61
    • 84986654269 scopus 로고
    • For some pioneering studies on the enantioselective preparation of quaternary carbon centres from 3,3-disubstituted allylboronates, see: (a) Hoffmann, R. W.; Schlapbach, A. Liebigs Ann. Chem. 1991, 1203-1206.
    • (1991) Liebigs Ann. Chem. , pp. 1203-1206
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    • For the previously reported Lewis acid-catalyzed formation of a reactive difluoroborane (a reaction which marks the first formal catalysed allylboration), see: (a) Batey, R. A.; Thadani, A. N.; Smil, D. V. Tetrahedron Lett. 1999, 40, 4289-4292.
    • (1999) Tetrahedron Lett. , vol.40 , pp. 4289-4292
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    • note
    • While the difference in reaction rates between the scandium-catalyzed reactions in the presence and absence of diisopropylethylamine might be due to a sequestering of the catalyst by the amine, it might also be due to competitive coordination of the amine to the boronate.
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    • There have been reports of the generation of carbocation intermediates from allylic and benzylic alcohols by Lewis acids. See: (a) Tsuchimoto, T.; Tobita, K.; Hiyama, T.; Fukuzawa, S.; J. Org. Chem. 1997, 62, 6997-7005.
    • (1997) J. Org. Chem. , vol.62 , pp. 6997-7005
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    • Analogously, Aggarwal and co-workers reported that the rate enhancement in the lanthanum triflate catalysed Baylis-Hillman reaction derives from enhanced hydrogen bonds between the substrate and coordinated hydroxyl groups on the Lewis acid rather than from direct binding of the lanthanide to the substrate. See: Aggarwal, V. K.; Mereu, A.; Tarver, G. J.; McCague, R. J. Org. Chem. 1998, 63, 7183-7189.
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