A Novel Asymmetric Hydroarsination Reaction Promoted by a Chiral Organopalladium Complex

Abstract

The dissymmetrical chiral bidentate (R)-(+)-1-(diphenylphosphino)-2-(diphenylarsino)propane was prepared stereoselectively via the novel asymmetric hydroarsination reaction between diphenylarsine and diphenyl-1-propenyl-(E)-phosphine using di-mu-chlorobis{(S)-1-[1-(dimethylamino)ethyl]-2-naphthalenyl-C,N}dipalladium(II) as the chiral reaction promoter.

Asymmetric hydroarsination reactions toward synthesis of alcohol functionalised C-chiral As–P ligands promoted by chiral cyclometallated complexes

“…The perchlorato complex (Rc)-3a was then treated with diphenylarsine at À78 C and the reaction mixture was then left to stir for 24 h. The reported conditions are the optimum condition for this reaction and have also been used extensively in our previous works on asymmetric hydrophosphination [9] and hydroarsination reactions [5]. The 31 P NMR spectrum showed a singlet at d 77.6 indicating that only one diastereomer was generated out of the two possible diastereomers.…”

“…However available methods to prepare arsine ligands are limited [2] and the number of reports on the addition of AseH moiety to a CeC double bond of an unsaturated compound is not vastly reported [3]. Applying chiral cyclometallated complexes as efficient chiral auxiliaries, our group has recently published reports on the synthesis of an optically active AseP heterobidentate ligand via DielseAlder cycloaddition [4] and asymmetric hydroarsination reaction [5]. Keto and ester-functionalised chiral pyridyl-arsines has also been synthesised via a similar reaction by our group [6].…”

Chiral palladacycle promoted asymmetric synthesis of functionalized bis-phosphine monoxide ligand

“…Over the past few years, our group has reported the use of chiral cyclometalated-amine complexes as efficient promoters for asymmetric synthesis of chiral phosphines by means of DielseAlder reactions [19e22], hydroamination reactions [23], hydrophosphination reactions [24e28] and hydroarsination reactions [29]. Asymmetric oxidation of polyphosphines has also been studied [30].…”

Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S Ligand

“…of such chiral systems incorporating As and P moieties with a view to understanding the subtle but significant variations in the chemistry of arsenic (vs. phosphorus) exhibited in such reaction scenarios. [13][14][15][16][17][18] …”