13639-74-2Relevant articles and documents
Haake et al.
, p. 2650,2652 (1967)
Indolizy Carbene Ligand. Evaluation of Electronic Properties and Applications in Asymmetric Gold(I) Catalysis
Fensterbank, Louis,Forté, Jérémy,Gontard, Geoffrey,Lemière, Gilles,Martinez, Thibaut,Mouriès-Mansuy, Virginie,Troufflard, Claire,Vanitcha, Avassaya,Vanthuyne, Nicolas
supporting information, p. 19879 - 19888 (2021/08/06)
We report herein a new family of carbene ligands based on an indolizine-ylidene (Indolizy) moiety. The corresponding gold(I) complexes are easily obtained from the gold(I)-promoted cyclization of allenylpyridine precursors. Evaluation of the electronic pr
Mixed (P=S/P=O)-stabilized geminal dianion: Facile diastereoselective intramolecular C-H activations by a related ruthenium-carbene complex
Heuclin, Hadrien,Le Goff, Xavier F.,Mezailles, Nicolas
, p. 16136 - 16144 (2013/02/23)
A new unsymmetrical geminal dianion that contained both a phosphine oxide moiety and a phosphine sulfide moiety has been synthesized. Its reactivity towards RuII was explored, which led to the formation of a highly reactive carbene complex that evolved at room temperature to yield a kinetic orthometalated RuII complex through C-H activation of the phenyl group of the phosphine oxide moiety. This insertion was found to be thermally reversible and a second C-H insertion occurred at a phenyl group of the phosphine sulfide moiety to form the thermodynamic orthometalated Ru II complex in a diastereospecific manner. DFT calculations fully rationalized the experimental findings in terms of the relative energies of the kinetic and thermodynamic products and allowed the mechanism of this process to be fully understood.
The lithiation and acyl transfer reactions of phosphine oxides, sulfides and boranes in the synthesis of cyclopropanes
Clarke, Celia,Fox, David J.,Pedersen, Daniel Sejer,Warren, Stuart
supporting information; experimental part, p. 1329 - 1336 (2009/12/04)
Phosphine oxides are lithiated much faster than phosphine sulfides and phosphine boranes. Phosphine sulfides are in turn lithiated much more readily than phosphine boranes. It was possible to trap a phosphine sulfide THF in one case which upon treatment with t-BuOK gave cyclopropane, showing that phosphine sulfides readily undergo both phosphinoyl transfer and cyclopropane ring closure just like their phosphine oxide counterparts. The obtained data show that phosphine oxides are easily lithiated and undergo phosphoryl transfer much more readily and faster than phosphine sulfides and phosphine boranes. The observations suggest that it would be possible to perform reactions involving phosphine oxides in the presence of phosphine boranes or phosphine sulfides, potentially allowing regioselective alkylation of phosphine oxides in the presence of phosphine boranes or phosphine sulfides.
