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1.Activation of C_F Bonds in Preference to C_I  Bonds£ºDifluoromethylation of Lithium Enolates with Trifluoromethyl Iodide
2.During the course of our research on a-trifluoromethylation[
18] of metal enolates catalyzed by late-transition-metal
complexes, a-difluoromethyl products were obtained using
lithium enolates (Figure 1), but without the need for any latetransition-
metal catalyst such as nickel complexes.
3. 3-benzyldihydrofuran-2-one          4. LHMDS
5£¬difluoromethyl-attached all-carbon quaternary centers
6. Potassium and  ¡°naked¡± enolates prepared from the trimethylsilyl enol ether
and tetra-n-butylammonium fluoride (TBAF) did not give
any a-difluoromethyl product at all. It is highly likely that this
a-difluoromethylation takes place through the interaction of
the Lewis acidic lithium center with fluoride in preference to
iodide.
7. LDA        8. LTDDS       9£¬LTMP
10£¬Amine-free lithium enolate
prepared from the trimethylsilyl enol ether and nBuLi[22] was
also investigated and found to give 1a in 68% yield (Table 1, entry 9),
11. diisopropylamine-free
12£¬TriMEDA
13£¬The highlight of the present report is the synthesis of the a-difluoromethylated analogue of  ibuprofen with retention of the analgesic activity even with
non-epimerizable all-carbon quaternary centers
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2Â¥2011-12-17 21:59:50
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3Â¥2011-12-17 22:13:31
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°®ÓëÓêÏÂ(½ð±Ò+1): 2011-12-18 08:43:24
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LHMDS£ºLithium Bis(trimethylsilyl)amide
TBAF£ºTetra-n-butylammonium fluoride
LDA£ºLithium diisopropylamide
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4Â¥2011-12-17 22:25:27
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°®ÓëÓêÏÂ(½ð±Ò+1): 2011-12-18 19:49:10
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LHMDS£ºLithium HexaMethylDiSilazide

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