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Nucleophilic α-Arylation and α-Alkylation of Ketones by Polarity Inversion of N-Alkoxyenamines: Entry to the Umpolung Reaction at the α-Carbon Position of Carbonyl Compounds. -The efficient and transition metal free umpolung reaction by polarity inversion at the β-position of N-alkoxyenamines is characterized by mild conditions and simple transformation of ketones such as (I) into α-substituted ketones (IV) without isolation of the intermediate enamine derivatives (II). Variants of this reaction allow the one-pot double nucleophilic reaction [→ (XVI)] or the simplified one-pot enamine formation without MgSO4 and following umpolung arylation [→ (XVIII)]. -(MIYOSHI, T.; MIYAKAWA, T.; UEDA, M.; MIYATA*, O.; Angew. Chem., Int. Ed. 50 (2011) 4, 928-931, http://dx.doi.org/10.1002/anie.201004374 ; Kobe Pharm. Univ., Higashinada, Kobe 658, Japan; Eng.) -Kieslich