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Volumn 129, Issue 48, 2007, Pages 14856-14857

Copper-catalyzed enantioselective substitution of allylic carbonates with diboron: An efficient route to optically active α-chiral allylboronates

Author keywords

[No Author keywords available]

Indexed keywords

BORON; BORONIC ACID DERIVATIVE; CARBONIC ACID; COPPER; LIGAND;

EID: 36849074311     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja076634o     Document Type: Article
Times cited : (241)

References (32)
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    • Hoffmann, R.W.1
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    • (c) Boronic Acids; Hall, D. G., Ed.; Wiley-VCH Verlag: Weinheim, Germany, 2000.
    • (2000) Boronic Acids
  • 4
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    • For the selected synthesis of a-chiral allylboronates with chiral auxiliary, see: a
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    • Hoffmann, R.W.1
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    • For the synthesis of a-chiral allylboronates through asymmetric catalysis, see: a
    • For the synthesis of a-chiral allylboronates through asymmetric catalysis, see: (a) Gao, X.; Hall, D. G. J. Am. Chem. Soc. 2003, 125, 9308-9309.
    • (2003) J. Am. Chem. Soc , vol.125 , pp. 9308-9309
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    • For studies on reactions of boryl nucleophiles, see: a
    • For studies on reactions of boryl nucleophiles, see: (a) Ito, H.; Yamanaka, H.; Tateiwa, J.; Hosomi, A. Tetrahedron Lett. 2000, 41, 6821-6825.
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  • 18
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    • For transition metal-catalyzed allylic substitution with diboron, see: a
    • For transition metal-catalyzed allylic substitution with diboron, see: (a) lto, H.; Kawakami, C.; Sawamura, M. J. Am. Chem. Soc. 2005, 127, 16034-16035.
    • (2005) J. Am. Chem. Soc , vol.127 , pp. 16034-16035
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  • 21
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    • For studies on boryllithiums and borylmagnesiums, see: a
    • For studies on boryllithiums and borylmagnesiums, see: (a) Segawa, Y.; Yamashita, M.; Nozaki, K. Science 2006, 314, 113-115.
    • (2006) Science , vol.314 , pp. 113-115
    • Segawa, Y.1    Yamashita, M.2    Nozaki, K.3
  • 23
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    • For borylation of activated alkenes catalyzed by a chiral Cu(I) complex, see: Mun, S.; Lee, J.; Yun, J. Org. Lett. 2006, 8, 4887-4889.
    • For borylation of activated alkenes catalyzed by a chiral Cu(I) complex, see: Mun, S.; Lee, J.; Yun, J. Org. Lett. 2006, 8, 4887-4889.
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    • For reviews of copper-catalyzed asymmetric allylic alkylation, see: a
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    • (2005) Angew. Chem., Int. Ed , vol.44 , pp. 4435-4439
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  • 27
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    • No reaction occurred when R is a cyclohexyl group
    • No reaction occurred when R is a cyclohexyl group.
  • 28
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    • For Lewis acid-mediated reactions of allylboronates with aldehydes, see: a
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  • 30
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    • For experimental and theoretical studies on addition of neutral borylcopper(I) species across C-C double bonds, see: (a) Laitar, D. S.; Tsui, E. Y.; Sadighi, J. P. Organometallics 2006, 25, 2405-2408.
    • For experimental and theoretical studies on addition of neutral borylcopper(I) species across C-C double bonds, see: (a) Laitar, D. S.; Tsui, E. Y.; Sadighi, J. P. Organometallics 2006, 25, 2405-2408.
  • 32
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    • The involvement of (π-allyl)copper(III) species, which are key intermediates in allylic substitution with diorganocuprates, is unlikely. The neutral boryl-copper species (B) should be less reactive toward oxidative addition than anionic diorganocuprates owing to lower nucleophilicity. See: Yamanaka, M.; Kato, S.; Nakamura, E. J. Am. Chem. Soc. 2004, 126, 6287-6293.
    • The involvement of (π-allyl)copper(III) species, which are key intermediates in allylic substitution with diorganocuprates, is unlikely. The neutral boryl-copper species (B) should be less reactive toward oxidative addition than anionic diorganocuprates owing to lower nucleophilicity. See: Yamanaka, M.; Kato, S.; Nakamura, E. J. Am. Chem. Soc. 2004, 126, 6287-6293.


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