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c) K. C. Nicolaou, K. B. Simonsen, G. Vassilikogiannakis, P. S. Baran, V. P. Vidali, E. N. Pitsinos, E. A. Couladouros, Angew. Chem. 1999, 111, 3762;
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f) A. Nakazaki, T. Era, Y. Numada, S. Kobayashi, Tetrahedron 2006, 62, 6264;
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g) A. Srikrishna, V. H. Pardeshi, G. Satyanarayana, Tetrahedron Lett. 2007, 48, 4087;
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10
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33750969372
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for the catalytic enantioselective alkylative aldol reaction of allenic esters and ketones with dialkyl zinc reagents towards the synthesis of functionalized δ-lactones, see: h D. Zhao, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 14440
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for the catalytic enantioselective alkylative aldol reaction of allenic esters and ketones with dialkyl zinc reagents towards the synthesis of functionalized δ-lactones, see: h) D. Zhao, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 14440.
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b) A. Srikrishna, D. H. Dethe, P. R. Kumar, Tetrahedron Lett. 2004, 45, 2939;
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Srikrishna, A.1
Dethe, D.H.2
Kumar, P.R.3
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53249137328
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c) K. C. Nicolaou, D. Pappo, K. Y. Tsang, R. Gibe, D. Y.-K. Chen, Angew. Chem. 2008, 120, 958;
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Nicolaou, K.C.1
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36749007137
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Z. Lu, G. Chai, S. Ma, J. Am. Chem. Soc. 2007, 129, 14546.
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Lu, Z.1
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53549124804
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Crystal data for 2a: C26H28O3, Mr, 388.51, monoclinic, P121/c1, Mo Kα, final R indices (I > 2σ(I, R1, 0.0491, wR2, 0.1028, a, 10.4687(8, b, 14.8999(10, c, 14.6133(10) Å, α, 90, β, 103.0580(19, γ, 90°, V, 2220.5(3) Å3, Z, 4, number of reflections measured/unique: 5052/1585 (R int, 0.061, number of observations: 5051 (I > 2σ(I, 291 parameters. CCDC 672093 (2a) and CCDC 672094, 4S,6R)-2c) 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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int = 0.061), number of observations: 5051 (I > 2σ(I)), 291 parameters. CCDC 672093 (2a) and CCDC 672094 ((-)-(4S,6R)-2c) 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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18
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53549104592
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Crystal data for, 4S,6R)-2c: C 26H26Br2O3, Mr, 546.30, monoclinic, P1211, MoKα, final R indices (I > 2σ(I, R1, 0.0635, wR2, 0.1966, a =7.3758(4, b, 24.7978(13, c, 14.0258(7) Å, α, 90, β, 90.2228(14, γ, 90°, V, 2565.4(2) Å3, Z, 4, number of reflections measured/unique: 5956/3461 (Rint, 0.073, number of observations: 5956 (I > 2σI, 561 parameters
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int = 0.073), number of observations: 5956 (I > 2σ(I)), 561 parameters.
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19
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34548428596
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For a monograph on carbozincation, see: a, Eds, Z. Rappoport, I. Marek, Wiley, Chichester
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For a monograph on carbozincation, see: a) E. Lorthiois, C. Meyer, The Chemistry of Organozinc Compounds (Eds.: Z. Rappoport, I. Marek), Wiley, Chichester, 2006, pp. 863-977;
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(2006)
The Chemistry of Organozinc Compounds
, pp. 863-977
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Lorthiois, E.1
Meyer, C.2
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20
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0008086878
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2Zn to conjugated alkynes, see: b J. Auger, G. Courtois, L. Miginiac, J. Organomet. Chem. 1977, 133, 285;
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2Zn to conjugated alkynes, see: b) J. Auger, G. Courtois, L. Miginiac, J. Organomet. Chem. 1977, 133, 285;
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23
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84906287738
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for the anti addition of nucleophiles to allenoates, see: e Y. Naruse, S. Kakita, A. Tsunekawa, Synlett 1995, 711.
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for the anti addition of nucleophiles to allenoates, see: e) Y. Naruse, S. Kakita, A. Tsunekawa, Synlett 1995, 711.
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24
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0000373915
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In the reported crystal structure of the Reformatsky reagent (BrZnCH 2COOtBu·THF)2, the C-Zn bond was clearly visible: a) J. Dekker, P. H. M. Budzelaar, J. Boersma, G. J. M. van der Kerk, A. L. Spek, Organometallics 1984, 3, 1403;
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2, the C-Zn bond was clearly visible: a) J. Dekker, P. H. M. Budzelaar, J. Boersma, G. J. M. van der Kerk, A. L. Spek, Organometallics 1984, 3, 1403;
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25
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0345697835
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see also: b
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see also: b) J. Dekker, A. Schouten, P. H. M. Budzelaar, J. Boersma, G. J. M. van der Kerk, A. L. Spek, A. J. M. Duisenberg, J. Organomet. Chem. 1987, 320, 1;
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(1987)
J. Organomet. Chem
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, pp. 1
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Dekker, J.1
Schouten, A.2
Budzelaar, P.H.M.3
Boersma, J.4
van der Kerk, G.J.M.5
Spek, A.L.6
Duisenberg, A.J.M.7
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26
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0001537390
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for the configurational stability of organozinc reagents, see
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for the configurational stability of organozinc reagents, see: S. Klein, I. Marek, J. F. Normant, J. Org. Chem. 1994, 59, 2925.
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(1994)
J. Org. Chem
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Klein, S.1
Marek, I.2
Normant, J.F.3
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27
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53549122600
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We thank one of the referees for suggesting this mechanistic possibility
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We thank one of the referees for suggesting this mechanistic possibility.
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28
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53549127419
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The fact that we did not observe the formation of the six-membered product 2 during the studies described in ref. [3] indicates the lower reactivity of magnesium 1,3-dienolates towards 2,3-allenoates.
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The fact that we did not observe the formation of the six-membered product 2 during the studies described in ref. [3] indicates the lower reactivity of magnesium 1,3-dienolates towards 2,3-allenoates.
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29
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53549111456
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The reaction of optically active (-)-(R)-2a with RMgBr provided the racemic products of conjugate addition.
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The reaction of optically active (-)-(R)-2a with RMgBr provided the racemic products of conjugate addition.
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30
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33748542017
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For an uncatalyzed addition of a dialkyl zinc reagent to 2-alkenoates with a radical mechanism, see
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For an uncatalyzed addition of a dialkyl zinc reagent to 2-alkenoates with a radical mechanism, see: F. Denes, S. Cutri, A. Perez-Luna, F. Chemla, Chem. Eur. J. 2006, 12, 6506.
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(2006)
Chem. Eur. J
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, pp. 6506
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Denes, F.1
Cutri, S.2
Perez-Luna, A.3
Chemla, F.4
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