Open AccessYlide‐Functionalization via Metalated Ylides: Synthesis and Structural Properties
Author(s) -
Schwarz Christopher,
Scherpf Thorsten,
Rodstein Ilja,
Weismann Julia,
Feichtner KaiStephan,
Gessner Viktoria H.
Publication year - 2019
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201900094
Subject(s) - ylide , substituent , electrophile , chemistry , steric effects , nucleophile , surface modification , medicinal chemistry , combinatorial chemistry , stereochemistry , organic chemistry , catalysis
Abstract The α‐metallated ylides [Ph 3 P−C−Z] − M + (with Z=SO 2 Tol 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.