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To date, only a Rh-catalyzed asymmetric conjugate addition of aryl boron reagents to α,β-unsaturated esters has been reported, but the method is intrinsically unsuitable for the direct addition of alkyl groups: a) S. Sakuma, M. Sakai, R. Itooka, N. Miyaura, J. Org. Chem. 2000, 65, 5951-5955;
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2942635094
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For an explanation of the reactivity of α,β-unsaturated carboxylic acid derivatives relative to that of enones on the basis of their respective LUMO energies, see: S. Matsunaga, T. Kinoshita, S. Okuda, S. Harada, M. Shibasaki, J. Am. Chem. Soc. 2004, 126, 7559-7570.
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0141725892
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For selected recent examples, see: a) M. S. Taylor, E. N. Jacobsen, J. Am. Chem. Soc. 2003, 125, 11 204-11 205, and references therein;
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0141732263
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d) M. P. Sibi, N. Prabagaran, S. G. Ghorpade, C. P. Jasperse, J. Am. Chem. Soc. 2003, 125, 11 796-11 797, and references therein;
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18844374869
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note
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e) see also references [1a] and [1e].
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0037451410
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0035926420
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With other alkyl zinc reagents only modest selectivities were observed; see also: A. Alexakis, C. Benhaim, Tetrahedron: Asymmetry 2001, 12, 1151-1157.
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5644222576
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40
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18844400635
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note
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a) For enantioselective additions of Grignard reagents to lactones, see references [14a] (5 mol% catalyst: 47-82% ee) and [4c] (32 mol% catalyst: 76-90% ee).
-
-
-
-
41
-
-
0003128726
-
-
and references therein
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H.-U. Blaser, W. Brieden, B. Pugin, F. Spindler, M. Studer, A. Togni, Top. Catal. 2002, 19, 3-16, and references therein.
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Blaser, H.-U.1
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42
-
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18844438384
-
-
note
-
A further decrease in the catalyst loading to 0.05 mol% (S/C = 2000:1) still led to 3a with a remarkable 86% ee and 70% conversion (GC-MS).
-
-
-
-
43
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0041701459
-
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Compound 4 a was recovered in 82% yield. For related achiral halogen-bridged dinuclear Cu species, see: a) E. D. Blue, A. Davis, D. Conner, T. B. Gunnoe, P. D. Boyle, P. S. White, J. Am. Chem. Soc. 2003, 125, 9435-9441;
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37049077763
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b) S. P. Neo, Z-Y. Zhou, T. C. W. Mak, T. S. A. Hor, J. Chem. Soc. Dalton Trans. 1994, 3451-3458, and references therein.
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Neo, S.P.1
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45
-
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18844407573
-
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note
-
2 in acetonitrile and converted into the dimeric complex 4a by treatment with halogenated solvents. See Supporting Information for the characterization of 4a and 4a′ and further information.
-
-
-
-
46
-
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18844444291
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-
CCDC 261573 contains 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.
-
-
-
-
47
-
-
18844450501
-
-
note
-
Sterically hindered Grignard reagents, such as iPrMgBr, and aryl Grignard reagents, such as PhMgBr, have provided poor results so far. (iPrMgBr: 26% conversion, 12% ee; PhMgBr: 55% conversion, 1% ee.)
-
-
-
-
48
-
-
18844367215
-
-
note
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See Supporting Information for details.
-
-
-
-
49
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0038567454
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For a Review on olefin cross-metathesis, see: a) S. J. Connon, S. Blechert, Angew. Chem. 2003, 115, 1944-1968;
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Angew. Chem. Int. Ed. 2003, 42, 1900-1923.
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51
-
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18844367762
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note
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2 was prepared by the method shown in Scheme 2 and used in these reactions. The same results were obtained when 4b was prepared in situ.
-
-
-
|