73106-85-1Relevant academic research and scientific papers
Synthesis, Structure, and Solution Studies of Lithiated Allylic Phosphines and Phosphine Oxides
Eren, Nimrod M.,Orr, Samantha A.,Thompson, Christopher D.,Border, Emily C.,Stevens, Michael A.,Blair, Victoria L.
, p. 2080 - 2090 (2020/06/05)
This study reports a new series of 12 α-lithiated allylic phosphines and phosphine oxides. By incorporating Lewis base donors including diethyl ether (Et2O), tetrahydrofuran (THF), N,N,N′,N′,-tetramethylethylenediamine (TMEDA), and N,N,N′,N′,N″,-pentamethyldiethylenetriamine (PMDETA), nine complexes were structurally characterized by single-crystal X-ray crystallography. This includes novel dilithiated allylic phosphine 4 [PhP{CHCHCH2Li(TMEDA)}2] and a rare hemisolvated lithiated phosphine oxide 6 [{Ph2P(O)CHC(Me)CH2Li}2(TMEDA)]. Interestingly, in the solid state, P(III) complexes take advantage of Li-πinteractions to the newly formed delocalized system, in comparison to P(V) complexes where the oxophillic nature of the lithium atom dominates. All 12 complexes were fully characterized in the solution state by multinuclear NMR spectroscopy. DFT calculations on isomers of monomeric lithiated complex 3 [Ph2PCHC(Me)CH2Li(PMDETA)] described the low energy barrier between transition steps of the subtle delocalization of the allylic chain.
Kinetic resolution of planar-chiral (η6-arene)chromium complexes by molybdenum-catalyzed asymmetric ring-closing metathesis
Ogasawara, Masamichi,Wu, Wei-Yi,Arae, Sachie,Watanabe, Susumu,Morita, Tomotaka,Takahashi, Tamotsu,Kamikawa, Ken
supporting information; experimental part, p. 2951 - 2955 (2012/05/20)
Molybdenum-catalyzed asymmetric ring-closing metathesis has been used for the kinetic resolution of racemic planar-chiral (η6-arene) chromium complexes with excellent enantioselectivity. The products are excellent precursors for the synthesis of various planar-chiral (η6-arene) chromium derivatives and can also be applied as chiral ligands in rhodium-catalyzed asymmetric reactions. Copyright
