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p-Toluenesulfonylnitrile is commercially available.
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19744361925
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note
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However, the intermediates in this scheme so far remain unidentified.
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49
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19744373017
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note
-
When the reaction was quenched at a lower temperature (-50 °C), sulfonylpyridine 24b became a major constituent (24b and 24a in 37 and 28% yields, respectively).
-
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50
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19744365869
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note
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For additional control experiments and discussion, see the Experimental Section.
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19744367839
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note
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This may come from lower α acidity of 90 as compared to that of 44 or 84. Moreover, the irreversible elimination of the most reactive bromo group (among 90, 44, and 84) from titanated 90 should force the titanium transfer reaction from 91 to 90.
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