Synthesis and Evaluation of Side-Arm-Alkylated Phosphametallocene Phosphines

Carmichael, Duncan; Klankermayer, Jürgen; Müller, E.; Pietrusiewicz, K. Michał; Ricard, Louis; Seeboth, Nicolas; Sowa, Sylwia; Stankevič, M.

doi:10.1021/om100845p

Cited by 12 publications

(2 citation statements)

References 83 publications

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“…Phosphametallocene‐2,5‐bis(2′‐acylphospholide) 8 , which promised to meet our synthetic requirements, could be prepared quite straightforwardly (Scheme ) from the readily available phosphaferrocene‐2,5‐diester 4 24. Compound 4 was expeditiously transformed into diacid 5 in excellent yield (92 %) and then converted essentially quantitatively into the corresponding 2,5‐di(acylchloride) 6 under treatment with PCl 5 , in both cases by using well‐precedented technology 25,26. Reaction of 6 with the 2‐ester‐substituted phospholide 7 provided the target phosphaferrocene‐2,5‐bis(2′‐acyl phospholide) 8 cleanly, the transformation probably involving a nucleophilic attack of the phospholide phosphorus upon the acyl chloride followed by a rapid Toullec–Mathey type [1,5]‐shift/deprotonation step, with excess 7 acting as the base 27,28.…”

Section: Resultsmentioning

confidence: 99%

Oligo(metallocene)s Containing Keto‐Bridged Phospholyl Rings

2013

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Section: Resultsmentioning

confidence: 99%

Oligo(metallocene)s Containing Keto‐Bridged Phospholyl Rings

2013

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“…The requisite 2-(carbonyl-2′-phospholide)phosphametallocene skeleton was prepared easily through treatment of the known Ru (18b) 29 or new Fe (18a) 2-(chlorocarbonyl)-phosphametallocenes with phospholide 21. A rapid [1,5]-shift followed by a deprotonation, wherein a second equivalent of phospholide anion 21 serves as the base, allows the desired 2-(carbonyl-2′phospholide) phosphametallocene 20 to be prepared in one pot (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

et al. 2012

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Enantiopure 2-(chlorocarbonyl)phosphametallocenes [MCp*(2-{COCl}-3,4-Me(2)-5-Ph-PC(4))] (M = Fe, Ru) react with phospholide anions to give 2-phosphametallocene-2'-acylphospholides K[MCp*(2-CO-2'-{3',4'-Me(2)-5'-PhPC(4)}-3,4-Me(2)-5-Ph-PC(4))] (M = Fe, Ru) and these have been converted into keto-bis-(2-phosphametallocene)s through reaction with [FeClCp*(tmeda)]; templation of this process with CuBr gives rise to the C(2)- (or pseudo-C(2)- when M = Ru) symmetric form of [{MCp*(3,4-Me(2)-5-Ph-PC(4))}(2)-2,2'-(CO)] (M = Fe, Ru; Fe, Fe) with high (>95%) diastereoselectivity. X-Ray structures of these ligands coordinated to [RuCp*Cl] and [PtCl(2)] centres show that the spatial orientation of the very flexible keto-bis-(2-phosphametallocene) structure is highly responsive to the coordination sphere of the chelated platinum or ruthenium centre.

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Enantiomerically Pure Phosphaalkene–Oxazolines (PhAk‐Ox): Synthesis, Scope and Copolymerization with Styrene

Dugal-Tessier

Serin

Castillo-Contreras

et al. 2012

Chemistry A European J

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The design of a synthetic route to a class of enantiomerically pure phosphaalkene-oxazolines (PhAk-Ox) is presented. The condensation of a lithium silylphosphide and a ketone (the phospha-Peterson reaction) was used as the P=C bond-forming step. Attempted condensation of PhC(=O)Ox (Ox = CNOCH(iPr)CH(2)) and MesP(SiMe(3))Li gave the unusual heterocycle (MesP)(2)C(Ph)=CN-(S)-CH(iPr)CH(2)O (3). However, PhAk-Ox (S,E)-MesP=C(Ph)CMe(2)Ox (1 a) was successfully prepared by treating MesP(SiMe(3))Li with PhC(=O)CMe(2)Ox (52 %). To demonstrate the modularity and tunability of the phospha-Peterson synthesis several other phosphaalkene-oxazolines were prepared in an analogous manner to 1 a: TripP=C(Ph)CMe(2)Ox (1 b; Trip = 2,4,6-triisopropylphenyl), 2-iPrC(6)H(4)P=C(Ph)CMe(2)Ox (1 c), 2-tBuC(6)H(4)P=C(Ph)CMe(2)Ox (1 d), MesP=C(4-MeOC(6)H(4))CMe(2)Ox (1 e), MesP=C(Ph)C(CH(2))(4)Ox (1 f), and MesP=C(3,5-(CF(3))(2)C(6)H(3))C(CH(2))(4)Ox (1 g). To evaluate the PhAk-Ox compounds as prospective precursors to chiral phosphine polymers, monomer 1 a and styrene were subjected to radical-initiated copolymerization conditions to afford [{MesPC(Ph)(CMe(2)Ox)}(x){CH(2)CHPh}(y)](n) (9 a: x = 0.13n, y = 0.87n; GPC: M(w) = 7400 g mol(-1) , PDI = 1.15).

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Synthesis and Evaluation of Side-Arm-Alkylated Phosphametallocene Phosphines

Cited by 12 publications

References 83 publications

Oligo(metallocene)s Containing Keto‐Bridged Phospholyl Rings

Oligo(metallocene)s Containing Keto‐Bridged Phospholyl Rings

Diastereoselective synthesis and coordination chemistry of enantiopure keto-bis-(2-phosphametallocene)s

Enantiomerically Pure Phosphaalkene–Oxazolines (PhAk‐Ox): Synthesis, Scope and Copolymerization with Styrene

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