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Upstream product

• 676-83-5 methyldichlorophosphane 
• 108894-99-1 (2,4,6-triisopropylphenyl)magnesium bromide 

Downstream Products

• 104108-09-0 Methyl-phenyl-(2,4,6-triisopropyl-phenyl)-phosphane 

Relevant academic research and scientific papers

Rhodium-Catalyzed Isomerization of a Bis(secondary phosphine) to an Unsymmetrical Diphosphine via P-C Cleavage and P-P and C-H Bond Formation

To develop Rh-catalyzed dehydrocoupling for stereocontrolled synthesis of P-P bonds, we prepared potential intermediates, chiral rhodium phosphine-phosphido complexes, and investigated their stoichiometric and catalytic transformations. Treatment of [Rh(diphos)(COD)][X] with the bis(secondary phosphine) IsHPCH2PHIs (1, Is = 2,4,6-(i-Pr)3C6H2) gave the cations [Rh(diphos)(IsHPCH2PHIs)][X] (diphos? = (R,R)-Me-DuPhos (2), (R,R)-i-Pr-DuPhos (3), or (R,R)-Me-BPE (4); X = BF4 or OTf) with high diastereoselectivity as single C2-symmetric diastereomers. Deprotonation of 2-4 with NaN(SiMe3)2 yielded phosphine-phosphido chelates Rh(diphos)(IsHPCH2PIs) 5-7 with high diastereoselectivity. Thermolysis of 5-7 in toluene at 90 °C caused isomerization to give Rh(diphos)(IsMeP-PIs) (8-10) as mixtures of diastereomers. Under catalytic conditions, Rh-DuPhos precursors slowly converted 1 to a mixture of diastereomers of its isomer, the unsymmetrical diphosphine IsHP-PMeIs (12). We propose a possible mechanism for the isomerization and discuss its relationship to dehydrocoupling catalysis.

Diastereoselective Coordination of P-Stereogenic Secondary Phosphines in Copper(I) Chiral Bis(phosphine) Complexes: Structure, Dynamics, and Generation of Phosphido Complexes

Diastereoselective coordination of racemic secondary phosphines (PHRR′) to Cu(I) precursors containing chiral bis(phosphines) (diphos*) was explored as a potential route to P-stereogenic phosphido complexes. Reaction of [Cu(NCMe)4][PF6] with chiral bis(phospholanes) gave [Cu(diphos*)2][PF6] (diphos? = (R,R)-Me-DuPhos (1), (R,R)-Et-DuPhos (2), or (R,R)-Me-FerroLANE) (3)) or the mono(chelates) [Cu(diphos*)(NCMe)n][PF6] (diphos? = (R,R)-i-Pr-DuPhos, n = 2 (4); diphos? = (R,R)-Me-FerroLANE, n = 1 (5)). Treatment of [Cu(NCMe)4][PF6] with diphos? and PHMe(Is) (Is = 2,4,6-(i-Pr)3C6H2) gave mixtures of diastereomers of [Cu((R,R)-i-Pr-DuPhos)(PHMe(Is))(NCMe)][PF6] (6) and [Cu((R,R)-Me-FerroLANE)(PHMe(Is))][PF6] (7); two of the three expected isomers of the bis(secondary phosphine) complexes [Cu((R,R)-i-Pr-DuPhos)(PhHP(CH2)nPHPh)][PF6] (n = 2 (8); n = 3 (9)) were formed preferentially in related reactions. Reaction of the halide-bridged dimers [Cu((R,R)-i-Pr-DuPhos)(X)]2 or [Cu((R,R)-Me-FerroLANE)(I)]2 with PHMe(Is) gave the labile adducts Cu((R,R)-i-Pr-DuPhos)(PHMe(Is))(X) (X = Cl (10), Br (11), I (12)) and Cu((R,R)-Me-FerroLANE)(PHMe(Is))(I) (13). Complexes 1, 6, and 8-11 were structurally characterized by X-ray crystallography. Variable temperature NMR studies of 6 and 8 showed that the secondary phosphine ligands underwent reversible dissociation. Deprotonation of 6 or 7 generated the P-stereogenic phosphido complexes Cu(diphos*)(PMeIs) (diphos? = (R,R)-i-Pr-DuPhos (14) or (R,R)-Me-FerroLANE) (17)), observed by 31P NMR spectroscopy, but decomposition also occurred. Density functional theory calculations were used to characterize the diastereomers of thermally unstable 17 and the inversion barrier in a model copper-phosphido complex. These observations provided structure-property relationships which may be useful in developing catalytic asymmetric reactions involving secondary phosphines and P-stereogenic copper phosphido intermediates.

Palladium-catalyzed asymmetric phosphination: Enantioselective synthesis of a P-chirogenic phosphine

The racemic secondary phosphine PH(Me)(Is) (1, Is = 2,4,6-(i-Pr)3C6H2) was coupled with PhI in the presence of NaOSiMe3 and the catalyst Pd((R,R)-Me-Duphos)(Ph)(I) (3) to give P(Ph)(Me)(Is) (2) in up to 78% ee.

Synthesis, Coordination Chemistry and Ligand Properties of Secondary Phosphines R(Ar*)PH with Bulky Aromatic Substituents - Molecular Structure of Ph(2,4,6-iPr3C6H2)PH, (2,4,6-iPr3C6H2)2PH and ClAu[PhP(2,4,6-tBu3C6H2)H]

The secondary phosphines R(Ar*)PH (R = Me, iPr, Ph, Mes, Ar*) (2a-2h) with bulky aromatic substituents Ar* (Ar* = 2,3,6-R′3C6H2, R′ = iPr, tBu) are obtained in good yields by reaction of RPCl2, PCl3, PBr3 or Ar*P(Cl,Br)2 with 2,4,6-tBu3C6H2Li or 2,4,6-iPr3C6H2MgBr and subsequent reduction of the intermediate halophosphines R(Ar*)PX (X = Cl, Br) with LiAlH4. The X-ray structural analysis of Ph(2,4,6-iPr3C6H2)PH (2g), space group P1, shows P-C-distances of 1.824(1) and 1.838(1)?. The lithium derivatives of 2a-2c are monomeric in solution as indicated by the 1 : 1 : 1 : 1-quartet 7Li-31P fine structure of the 31P{1H} NMR signals at low temperatures. 2a-2c and 2f-2h form Ni(0) and Fe(0) complexes (CO)3NiL (6a-6f) and Fe(CO)4L (7a-7d), respectively. The Tolman electronic parameters ν of the bulky ligands are almost identical. Within the series 2a-2h the spatial shielding of the P atoms has been estimated using advanced molecular modeling techniques. The bulky ligancl 2c forms coinage metal complexes [Cu(CH3CN)2(2c)2] [PF6] (8). Cu2Cl2(2c)2 (9) and Cl-Au(2c) (10). While 10 is monomeric in solution, in the solid state it forms pairs of head to tail oriented monomers with almost linear Cl-Au-P skeletons (Cl-Au-P 175.47(9)°) as shown by an X-ray structural analysis.