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Volumn 46, Issue 31, 2007, Pages 5909-5912

Catalytic activation of pinacolyl allylboronate with indium(I): Development of a general catalytic allylboration of ketones

Author keywords

Allylation; Boron; C C coupling; Indium; Ketones

Indexed keywords

ALLYLATION; CATALYTIC ACTIVATION;

EID: 34547769879     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200700899     Document Type: Article
Times cited : (81)

References (65)
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    • In contrast, indium(III) derivatives are commonly used in catalytic quantities as Lewis acid catalysts (see Ref. [6]).
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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.
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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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    • 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).
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    • 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.
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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.
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    • 8]THF, 40°C); however, conversion of ketone 1a into product 3a was not observed.
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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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    • 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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