Synthesis and catalytic properties of transition metal complexes with beta-cyclodextrin-functionalized phosphine ligands

Reaction of o-Ph₂PC₆H₄CHO with 6-H₂NCH₂CH₂NH-β-CD produced the potentially tridentate mixed donor iminophosphine β-cyclodextrin (6-( o-Ph₂PC₆H₄CH=NCH₂CH ₂NH)-β-CD) (CDNNP). Reactions of CDNNP with MCl₂(COD) (M = Pt, Pd) (COD = 1,5-cyclooctadiene) and [Pd(η3-C ₃H₅)Cl]₂ produced their platinum and palladium complexes.; Reaction of mono-6-trifluoromethanesulfonyl permethylated β-cyclodextrin with (2S,4S)-(−)-(diphenylphosphino)-2-(diphenylphosphinomethyl)-pyrrolidine in the presence of proton sponge in CH₂Cl₂ produced the mono-6-N-[4′-(diphenylphosphino)-2 ′-(diphenylphosphinomethyl)-pyrrolidinyl)]-6-deoxy permethylated β-cyclodextrin (PMβ-CDPPM). Mono-6-N-[4′-(diphenylphosphino)-2 ′-(diphenylphosphinomethyl)-pyrrolidinylmethyl-o-benzyl]-6-deoxy permethylated β-cyclodextrin (PMβ-CD-o-Ph-PPM) and mono-6-N-[4′-(diphenylphosphino)-2 ′-(diphenylphosphinomethyl)-pyrrolidinylmethyl-m-benzyl]-6-deoxy permethylated β-cyclodextrin (PMβ-CD-m-Ph-PPM) were also synthesized. Reactions of PtCl₂(COD) and [Rh(COD) ₂]BF₄ (COD = 1,5-cyclooctadiene) with PMβ-CDPPM, PMβ-CD- o-Ph-PPM and PMβ-CD-m-Ph-PPM produced their platinum and rhodium complexes.; 6A,6X-bis(trifluoromethanesulfonyl) permethylated β-cyclodextrins (X = B, C and D) were synthesized by the reactions of 6A,6 X-dihydroxy permethylated β-cyclodextrins (X = B, C and D) with trifluoromethanesulfonic anhydride in the presence of 2,4,6-tri(tert -butyl)pyridine. Reaction of mono-6-trifluoromethanesulfonyl permethylated β-cyclodextrin with LiPPh₂ produced monophosphine PMβ-CDP. Reactions of 6 A,6X-bis(trifluoromethanesulfonyl) permethylated β-cyclodextrins (X = B, C and D) with LiPPh₂ produced diphosphines 6A,6 X-PMβ-CDP2 (X = B, C and D). Reactions of 6A,6 X-PMβ-CDP2 (X = B, C and D) with [Rh(COD)₂]BF ₄ and PtCl₂(COD) (COD = 1,5-cyclooctadiene) produced their rhodium and platinum complexes.; (S,S)-4,5-Bis(diphenylphosphino)-2-(3′ -hydroxyphenyl)-1,3-dioxolane (m-OH-Bz-DIOP) was synthesized by the reaction of m-hydroxybenzaldehyde with (2S,3S)-dihydroxy-1,4-bis(diphenylphosphino)butane in the presence of p-toluenesulfonic acid in dry benzene. Reaction of (S,S)-4,5-Bis(diphenylphosphino)-2-(3 ′-hydroxyphenyl)-1,3-dioxolane with mono-6-trifluoromethanesulfonyl permethylated β-cyclodextrin in the presence of NaH in THF gave β-cyclodextrin-functionalized DIOP ligand (PMβ-CD-m-DIOP). The analogous ligand PMβ-CD- p-DIOP could be prepared by similar procedure starting from p-hydroxybenzaldehyde. Their rhodium and platinum complexes have been synthesized.; The β-cyclodextrin-functionalized phosphines have been evaluated for rhodium-catalyzed asymmetric hydrogenation, palladium-catalyzed allylic alkylation and palladium-catalyzed allylic amination.