Open AccessSynthesis, Crystal and Electronic Structures of a Thiophosphinoyl‐ and Amino‐Substituted Metallated Ylide
Author(s) -
Jörges Mike,
Kroll Alexander,
Kelling Leif,
Gauld Richard,
Mallick Bert,
Huber Stefan M.,
Gessner Viktoria H.
Publication year - 2021
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.202100187
Subject(s) - ylide , chemistry , dimer , lithium (medication) , moiety , monomer , delocalized electron , medicinal chemistry , main group element , stereochemistry , organic chemistry , transition metal , medicine , endocrinology , polymer , catalysis
α‐Metallated ylides have revealed themselves to be versatile reagents for the introduction of ylide groups. Herein, we report the synthesis of the thiophosphinoyl and piperidyl (Pip) substituted α‐metallated ylide [Ph 2 (Pip)P=C−P(S)Ph 2 ]M (M=Li, Na, K) through a four‐step synthetic procedure starting from diphenylmethylphosphine sulfide. Metallation of the ylide intermediate was successfully accomplished with different alkali metal bases delivering the lithium, sodium and potassium salts, the latter isolable in high yields. Structure analyses of the lithium and potassium compounds in the solid state with and without crown ether revealed different aggregates (monomer, dimer and hexamer) with the metals coordinated by the thiophosphoryl moiety and ylidic carbon atom. Although the piperidyl group does not coordinate to the metal, it significantly contributes to the stability of the yldiide by charge delocalization through negative hyperconjugation.