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In contrast to ketones, many allylation methods have been reported for aldehydes. For recent reviews on the allylation of aldehydes, see: a) A. Yanagisawa in Comprehensive Asymmetric Catalysis, Vol. 2 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999, pp. 965-979;
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Angew. Chem. Int. Ed. 2002, 41, 3697-3699;
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0037067020
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Use of a CuCl/TBAT catalyst and allylsilane (racemic version): S. Yamasaki, K. Fujii, R. Wada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2002, 124, 6536-6537.
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Use of a CuCl/TBAT catalyst and allylsilane (racemic version): S. Yamasaki, K. Fujii, R. Wada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2002, 124, 6536-6537.
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Use of a AgF/chiral diphosphine catalyst and allylsilane: M. Wadamoto, H. Yamamoto, J. Am. Chem. Soc. 2005, 127, 14 556-14 557.
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Use of a AgF/chiral diphosphine catalyst and allylsilane: M. Wadamoto, H. Yamamoto, J. Am. Chem. Soc. 2005, 127, 14 556-14 557.
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30
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34547743902
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For a stoichiometric method for enantioselective ketone allylation using a chiral strained allylsilane, see: N. Z. Burns, B. M. Hackman, P. Y. Ng, I. A. Powelson, J. L. Leighton, Angew. Chem. 2006, 118, 3895-3897;
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For a stoichiometric method for enantioselective ketone allylation using a chiral strained allylsilane, see: N. Z. Burns, B. M. Hackman, P. Y. Ng, I. A. Powelson, J. L. Leighton, Angew. Chem. 2006, 118, 3895-3897;
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Angew. Chem. Int. Ed. 2006, 45, 3811-3813.
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2/chiral diphosphine catalyst and allylboronate: R. Wada, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2004, 126, 8910-8911.
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2/chiral diphosphine catalyst and allylboronate: R. Wada, K. Oisaki, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2004, 126, 8910-8911.
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33
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33749514608
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Use of a chiral diol catalyst and allylboronate: S. Lou, P. N. Moquist, S. E. Schaus, J. Am. Chem. Soc. 2006, 128, 12 660-12 661.
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Use of a chiral diol catalyst and allylboronate: S. Lou, P. N. Moquist, S. E. Schaus, J. Am. Chem. Soc. 2006, 128, 12 660-12 661.
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34
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4344625966
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For stoichiometric methods for enantioselective ketone allylation using a chiral allylboronate or allylborane, see: a T. R. Wu, L. Shen, J. M. Chong, Org. Lett. 2004, 6, 2701-2704;
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For stoichiometric methods for enantioselective ketone allylation using a chiral allylboronate or allylborane, see: a) T. R. Wu, L. Shen, J. M. Chong, Org. Lett. 2004, 6, 2701-2704;
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36
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0008815194
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For recent reviews on the lower oxidation states of indium, see: a
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For recent reviews on the lower oxidation states of indium, see: a) D. G. Tuck, Chem. Soc. Rev. 1993, 22, 269-276;
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Tuck, D.G.1
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34547794181
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In contrast, indium(III) derivatives are commonly used in catalytic quantities as Lewis acid catalysts (see Ref. [6]).
-
In contrast, indium(III) derivatives are commonly used in catalytic quantities as Lewis acid catalysts (see Ref. [6]).
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40
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28044439192
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Angew. Chem. Int. Ed. 2005, 44, 7453-7456.
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R. J. Wright, A. D. Phillips, N. J. Hardman, P. P. Power, J. Am. Chem. Soc. 2002, 124, 8538-8539.
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34547747359
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For a recent highlight on this topic, see
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For a recent highlight on this topic, see: S. Aldridge, Angew. Chem. 2006, 118, 8275-8277;
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34547750435
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Indium(I) iodide is commercialized as 10-mesh beads, but the powdered form gave identical results.
-
Indium(I) iodide is commercialized as 10-mesh beads, but the powdered form gave identical results.
-
-
-
-
45
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34547776845
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The use of other allylboronates under the employed conditions proved to be less efficient than the use of pinacolyl allylboronate 2
-
The use of other allylboronates under the employed conditions proved to be less efficient than the use of pinacolyl allylboronate (2).
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46
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10044234065
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53
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34547734483
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The use of a smaller amount of allylboronate 2 (1.1 equiv, 20 mol % InI, 0.2 M in THF; or 1.0 equiv, 5 mol % InI, 0.5 M in THF) proved to be equally effective (90 % and 84 % yields, respectively) compared with conditions of entry 6 (Table 1; 1.5 equiv, 5 mol % InI, 0.2 M in THF, 88 % yield).
-
The use of a smaller amount of allylboronate 2 (1.1 equiv, 20 mol % InI, 0.2 M in THF; or 1.0 equiv, 5 mol % InI, 0.5 M in THF) proved to be equally effective (90 % and 84 % yields, respectively) compared with conditions of entry 6 (Table 1; 1.5 equiv, 5 mol % InI, 0.2 M in THF, 88 % yield).
-
-
-
-
54
-
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34547778482
-
-
It is notable that in all indium(I) iodide catalyzed experiments (Table 1, entries 2-7) no undesired compounds such as pinacol coupling type or reduction products were detectable in the crude reaction mixtures.
-
It is notable that in all indium(I) iodide catalyzed experiments (Table 1, entries 2-7) no undesired compounds such as pinacol coupling type or reduction products were detectable in the crude reaction mixtures.
-
-
-
-
55
-
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1642439198
-
-
Indium(I) triflate was prepared from commercially available indium(I) chloride and triflic acid in toluene at room temperature according to a known procedure: C. L. B. Macdonald, A. M. Corrente, C. G. Andrews, A. Taylor, B. D. Ellis, Chem. Commun. 2004, 250-251.
-
Indium(I) triflate was prepared from commercially available indium(I) chloride and triflic acid in toluene at room temperature according to a known procedure: C. L. B. Macdonald, A. M. Corrente, C. G. Andrews, A. Taylor, B. D. Ellis, Chem. Commun. 2004, 250-251.
-
-
-
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56
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34547812089
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-
On the other hand, use of 20 mol % indium(I) iodide in combination with trifluoroborate 4 (1.5 equiv) in the allylation of ketone 1a provided product 3a in only 41 % yield.
-
On the other hand, use of 20 mol % indium(I) iodide in combination with trifluoroborate 4 (1.5 equiv) in the allylation of ketone 1a provided product 3a in only 41 % yield.
-
-
-
-
57
-
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34547751408
-
-
8]THF, 40°C); however, conversion of ketone 1a into product 3a was not observed.
-
8]THF, 40°C); however, conversion of ketone 1a into product 3a was not observed.
-
-
-
-
58
-
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0037009989
-
-
Lewis acid activation of allylboronates of type 2 through coordination of a boronate alkoxy ligand to the corresponding Lewis acid has been reported. However, this catalytic method has been applied only to the use of aldehydes as electrophiles: a J. W. J. Kennedy, D. G. Hall, J. Am. Chem. Soc. 2002, 124, 11 586-11 587;
-
Lewis acid activation of allylboronates of type 2 through coordination of a boronate alkoxy ligand to the corresponding Lewis acid has been reported. However, this catalytic method has been applied only to the use of aldehydes as electrophiles: a) J. W. J. Kennedy, D. G. Hall, J. Am. Chem. Soc. 2002, 124, 11 586-11 587;
-
-
-
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59
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4544373510
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for a recent minireview on the activation of boron reagents, see
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b) for a recent minireview on the activation of boron reagents, see: J. W. J. Kennedy, D. G. Hall, Angew. Chem. 2003, 115, 4880-4887;
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Angew. Chem. Int. Ed. 2003, 42, 4732-4739;
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c) M. Gravel, H. Lachance, X. Lu, D. G. Hall, Synthesis 2004, 1290-1302;
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63
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34547801758
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For electrochemical in situ formation and regeneration of allylindium(I), see: G. Hilt, K. I. Smolko, Angew. Chem. 2001, 113, 3514-3516;
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For electrochemical in situ formation and regeneration of allylindium(I), see: G. Hilt, K. I. Smolko, Angew. Chem. 2001, 113, 3514-3516;
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64
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0035903687
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Angew. Chem. Int. Ed. 2001, 40, 3399-3402.
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Chem. Int. Ed
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34547776844
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Indium is known as a rare metal, thus catalytic use of indium is highly important: The Elements (Ed.: J. Emsley), 3rd ed., Oxford Press, Oxford, 1998.
-
Indium is known as a "rare metal", thus catalytic use of indium is highly important: The Elements (Ed.: J. Emsley), 3rd ed., Oxford Press, Oxford, 1998.
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-
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