Synthesis, resolution and reactions of (±)-(2-aminophenyl)methylphenylphosphine. Crystal and molecular structure of (R*,R*, S*, R*)-(±)-(1,3-bis{[2-(methylphenylphosphino)phenyl]amino}propane)nickel(II) perchlorate

Abstract

Synthesis, Resolution and Reactions of ( k )-(2-Amino-pheny1)methylphenylphosphine. Crystal and Molecular Structure of (R*,R*,S*,R*)-( k )-(I ,3-Bis{[2-(methylphenylphosphino)phenyl]amino}propane)nickeI( 11) Perchlorate t

Synthesis of 1,3-azaphosphol-2-ones. Crystal and molecular structures of [SP-4-2]-dichlorobis(3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one-P)palladium(ii) and its chloro(methyl)platinum(ii) analogue

“…The compounds (2-aminophenyl)diphenylphosphine, adpp, 1, 15 (±)-(2-aminophenyl)phenylphosphine, (±)-app, 2, 4 16 and [SP-4-2]-chloro(cycloocta-1,5-diene)methylplatinum(II), [PtClMe(cod)], 17 were prepared by literature procedures.…”

“…Tertiary phosphine (2-aminophenyl)diphenylphosphine, adpp, 1, is a versatile hybrid ligand that can be used to prepare a range of related bidentate PN and multidentate P 2 N 2 and very recently P 3 N 3 ligands via derivatisation of the amino or diphenylphosphino groups. 4 Derivatisation of the latter has typically been achieved via reductive cleavage of a phenyl group from adpp using three equivalents of lithium in thf or sodium in liquid ammonia, to give the secondary phosphine (±)-2-H 2 NC 6 H 4 PHPh, (±)-app, 2, upon hydrolysis followed by metallation with sodium in thf and alkylation with, for example, CH 3 I, Br(CH 2 ) n Br (where n = 3-6) or CH 3 C(CH 2 Br) 3 to give (±)-2-H 2 NC 6 H 4 PMePh, (R P *,R P *)and (R P *,S P *)-(CH 2 ) n (PPhC 6 H 4 NH 2 -2) 2 and (R P *,R P *,R P *)-and (R P *,R P *,S P *)-CH 3 C(CH 2 PPhC 6 H 4 NH 2 -2) 3 , respectively. [4][5][6] This approach typically, however, does not allow access to substituted (2-aminophenyl)phosphines of the type (±)-2-H 2 NC 6 H 4 PPhR (where R = aryl or vinyl group).…”

“…4 Derivatisation of the latter has typically been achieved via reductive cleavage of a phenyl group from adpp using three equivalents of lithium in thf or sodium in liquid ammonia, to give the secondary phosphine (±)-2-H 2 NC 6 H 4 PHPh, (±)-app, 2, upon hydrolysis followed by metallation with sodium in thf and alkylation with, for example, CH 3 I, Br(CH 2 ) n Br (where n = 3-6) or CH 3 C(CH 2 Br) 3 to give (±)-2-H 2 NC 6 H 4 PMePh, (R P *,R P *)and (R P *,S P *)-(CH 2 ) n (PPhC 6 H 4 NH 2 -2) 2 and (R P *,R P *,R P *)-and (R P *,R P *,S P *)-CH 3 C(CH 2 PPhC 6 H 4 NH 2 -2) 3 , respectively. [4][5][6] This approach typically, however, does not allow access to substituted (2-aminophenyl)phosphines of the type (±)-2-H 2 NC 6 H 4 PPhR (where R = aryl or vinyl group). A rare exception is the 2-chlorophenyl substituted PN ligand (±)-(2-aminophenyl)(2chlorophenyl)methylphosphine.…”

Synthesis, Coordination to Rh(I), and Hydroformylation Catalysis of New β-Aminophosphines Bearing a Dangling Nitrogen Group: An Unusual Inversion of a Rh-Coordinated P Center

“…Alkali metals are known to perform this reaction selectively and under mild conditions in ether or liquid NH3. [29][30][31] The presence of the secondary amine function in , 15 and gives rise to L 5A and L 5B in a ca. 3:2 ratio.…”

Chiral cyclopalladium (II) complexes promoted asymmetric synthesis of optically active functionalized bidentate phosphine ligands

“…Thus chiral chelating bidentate ligands including P-As (Scheme 1.35-1.37) 39 will coordinate to palladium(II) centre with phosphorus atom specifically occupied the trans position to nitrogen atom 39,40 . When it comes to P-N (Scheme 1.38-1.40) 13,41,42 and P-O (Scheme 1.41, 1.42) 43 ligands, the more efficient resolving reagent 20 was mostly utilized.…”