Ylide‐Functionalization via Metalated Ylides: Synthesis and Structural Properties

ChemistryOpen

Ilja Rodstein¹  Prof. Dr. Viktoria H. Gessner¹  Christopher Schwarz¹  Dr. Julia Weismann¹  Dr. Kai‐Stephan Feichtner¹  Dr. Thorsten Scherpf¹ 

[1] Chair of Inorganic Chemistry II Faculty of Chemistry and Biochemistry Ruhr University Bochum Universitätsstrasse 150 44801 Bochum Germany;

关键词: ylides;    carbanions;    alkali metals;    structure elucidation;    synthesis;   

DOI  :  10.1002/open.201900094

来源: DOAJ

【 摘 要 】

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.

【 授权许可】

Unknown