A series of mechanistic studies were performed to probe the existence of a ruthenium-catalyzed Brook rearrangement. Treatment of (benzoyl)tert-butyldimethylsilane (1 ) with RuH2(PPh3)4 under standard transfer hydrogenation conditions in the absence of base yielded the Brook rearrangement product 2  in 24% yield. Hydrogenation product 3  and tert-butyldimethylsilanol were also observed. Treatment of 1  with RuHCl(PPh3)4  yielded only 3  suggesting a dihydride mechanism may be operating. [1, 2] Brook rearrangements can occur with a catalyst operating with an outer or inner sphere mechanism.

Ruthenium-catalyzed Brook rearrangements for the rapid assembly of complex small molecules

245th National Meeting (2013)

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