Ylide‐Functionalization via Metalated Ylides: Synthesis and Structural Properties

• Main Authors: Christopher Schwarz, Dr. Thorsten Scherpf, Ilja Rodstein, Dr. Julia Weismann, Dr. Kai‐Stephan Feichtner, Prof. Dr. Viktoria H. Gessner
• Format: Article
• Language: English
• Published: Wiley-VCH 2019-05-01
• Series: ChemistryOpen
• Subjects: ylides; carbanions; alkali metals; structure elucidation; synthesis
• Online Access: https://doi.org/10.1002/open.201900094

Abstract The α‐metallated ylides [Ph3P−C−Z]−M+ (with Z=SO2Tol or CN and M=Na or K) were used as versatile nucleophiles for the facile access to ylide‐substituted compounds. Halogenations, alkylations, carbonylations and functionalization reactions with main group element halides were easily accomplished by simple trapping reactions with the appropriate electrophiles. X‐ray crystallographic studies of all compounds – including the first structures of α‐fluorinated P‐ylides – showed remarkable differences in the ylide backbone depending on the substituents. In the fluorinated compounds, a change from a fully planar to a pyramidalized ylidic carbon centre was observed despite the strongly anion‐stabilizing ability of the yldiide substituent. π‐Donation from the ylide substituent also resulted in geometric restrictions depending on the steric and electronic properties of the introduced substituents.