1062229-34-8Relevant articles and documents
Strategy for employing unstabilized nucleophiles in palladium-catalyzed asymmetric allylic alkylations
Trost, Barry M.,Thaisrivongs, David A.
supporting information; experimental part, p. 14092 - 14093 (2009/03/11)
We report a strategy for the employment of highly unstabilized anions in palladium-catalyzed asymmetric allylic alkylations (AAA). The hard 2-methylpyridyl nucleophiles studied are first reacted in situ with BF3?OEt2; subsequent deprotonation of the resulting complexes with LiHMDS affords soft anions that are competent nucleophiles in AAA reactions. The reaction is selective for the 2-position of methylpyridines and tolerates bulky aryl and alkyl substitution at the 3-, 4-, and 5-positions. Investigations into the reaction mechanism demonstrate that the configuration of the allylic stereocenter is retained, consistent with the canonical outer sphere mechanism invoked for palladium-catalyzed allylic substitution processes of stabilized anions.Copyright
