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Our procedure could not be applied to the generation of p-methoxysubstituted dianions 2, due to competitive demethoxyation reactions (see ref 2a).
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19
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0011618447
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The electrochemical behavior of 1b-d, under various conditions, was already reported. 1b: (a) 1c
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70350723137
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3 = -2.780 V vs. SCE). We assigned it to the formation of a pyridine-type radical anion. Indeed, pyridine itself is electrochemically reduced in DMF at -2.76 V vs. SCE; similarly, mono-, di-, and trimethylpyridines are reduced with E° ranging from -2.77 and -2.91 V vs. SCE:
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0003871081
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70350735290
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17c Disproportionation mechanisms, however, may provide the actual reaction path when very weak proton donors are present or added (such as alcohols or water): for example, see refs 11b and 4-7 and ref 10 cited therein.
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70350709454
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A reaction run with 1 equiv of 2d led to the recovery of a reaction mixture containing, besides 50% unreacted 4, 34% of 6a as well as 16% of 1,2-dihydxoxy-1,2,3,4-tetraphenylethane.
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38
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70350707057
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Reduction of ketoester 7 to ketoacid 8 was run with 1 equiv of dianion 2b under inverse addition reaction conditions (see the Supporting Information).
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39
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Under similar conditions, low conversions (12 to 13 and 14 to a mixture of 15 and 16) were observed performing these reactions in the presence of Na metal.
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