Catalyst efficiencies, lanthanide complexes

The discussion of the activation of bonds containing a group 15 element is continued in chapter five. D.K. Wicht and D.S. Glueck discuss the addition of phosphines, R2P-H, phosphites, (R0)2P(=0)H, and phosphine oxides R2P(=0)H to unsaturated substrates. Although the addition of P-H bonds can be sometimes achieved directly, the transition metal-catalyzed reaction is usually faster and may proceed with a different stereochemistry. As in hydrosilylations, palladium and platinum complexes are frequently employed as catalyst precursors for P-H additions to unsaturated hydrocarbons, but (chiral) lanthanide complexes were used with great success for the (enantioselective) addition to heteropolar double bond systems, such as aldehydes and imines whereby pharmaceutically valuable a-hydroxy or a-amino phosphonates were obtained efficiently. 

Heterogeneous diene polymerization catalysts based on modified and unmodified silica-supported lanthanide complexes are known as efficient gas-phase polymerization catalysts for a variety of support materials and activation procedures (see Sect. 9). Metal siloxide complexes M(()SiR3 )x are routinely employed as molecular model systems of such silica-immobilized/ grafted metal centers [196-199]. Structurally authenticated alkylated rare-earth metal siloxide derivatives are scarce, which is surprising given that structural data on a considerable number of alkylated lanthanide alkoxide and aryloxide complexes with a variety of substitution patterns is meanwhile available. 

Cationic lanthanide complexes have been found to be efficient catalysts for various organic transformations and polymerizations. The details are given in Section 8.6. 

Nitro-Aldol Condensation. A BINOL-derived lanthanide complex has been used as an efficient catalyst for the nitro-aldol reaction (eq 27). Interestingly enough, the presence of water and LiCl in the reaction mixture is essential to obtain the high level of asymmetric induction and chemical yield. 

L-Iduronyl synthons catalyzed by a vinyl cerium reagent have been shown to open a way to an efficient preparation of l,2,4-tri-0-acetyl-3-0-benzyl-Z,-iduronyl derivatives.1097 The synthetic utility of the cationic lanthanide complex [Cp 2Ce][BPh4] as an effective Lewis acid catalyst for the hetero-Diels-Alder reaction between Danishefsky s diene and substituted benzaldehydes has been demonstrated (Scheme 307). 

Anionic bridged bis(amidinate) lithium lanthanide complexes have been found to be efficient catalysts for the amidahon of aldehydes with amines under mild conditions (Scheme 56). The achvity was found to follow the order of yttrium < neodymium < europium ytterbium. The catalysts are available for the formahon of benzamides derived from pyrrolidine, piperidine, and morpholine with good to excellent yields. In comparison with the corresponding neutral complexes, the anionic complexes showed higher achvity and a wider range of scope for the amines. A cooperation of the lanthanide and lithium metals in this process was proposed to contribute to the high activity of these catalysts [66,67]. 

Sc(OTf)3 and Yb(( ) l r), are quite valuable catalysts of the aza-DA reaction of 102 [204] (Scheme 10.113). Wifh these catalysts, three-component coupling of aldehydes, anilines, and 102 proceeds smoothly [304]. Sc(OSO2C8Fi7)3 enables an efficient aza-DA reaction in supercritical CO2 [305]. Cationic lanthanide complexes, [(C5Me5)2Ce][BPh4] and fhe corresponding Sm and La complexes, have high catalytic activity in the HDA reaction of 102 with aromatic aldehydes [306]. 

Polymerization of diallg l vinylphosphonate monomers was nevertheless efficiently carried out in the presence of lanthanide derivatives and especially cyclopentadienyl lanthanide complexes, used both as initiators and catalysts. Very recently, Shen et al performed the synthesis of poly (diethyl vinylphosphonate) using a lanthanide tris(borohydride) below 50 °C. The authors showed that the polymerization eould be controlled and proceeds under pseudo-first-order kinetics, giving rise to high molecular weight polymers, i.e. ranging from 20 to 40 kDa with molecular weight dispersity below 1.7. 

To conclude this section, one should highlight recent studies on N-functionaUzed cyclopentadienyl ligands. The [(Cp )Ln(AlMe4)2] precatalysts (40), generated via a protonolysis reaction of Ln(AlMe4)3 with HCp (Scheme 24), were reported to be active in IP polymerization under various conditions (cocatalyst, solvent, temperature, time) and the best results are summarized in Table 3 [125]. Allyl-lanthanides complexes of an N-functionalized Cp (N = amino) were also reported by Cui et al. to be efficient catalysts for the living and block copolymerization of IP in the presence of organoaluminum (5-70 equiv.) and boron cocatalysts [126]. 

Mn(II) > Mg(II).270 It should be underlined that titanium and zirconium alkoxides are efficient catalysts for both stages of reaction. Lanthanide compounds such as 2,2/-bipyridyl, acetylacetonate, and o-formyl phenolate complexes of Eu(III), La(III), Sm(III), Er(III), and Tb(III) appear to be even more efficient than titanium alkoxides, Ca or Mn acetates, Sb203, and their mixtures.273 Moreover, PET produced with lanthanides has been reported to exhibit better thermal and hydrolytic stability as compared to PET synthesized with the conventional Ca acetate -Sb203 catalytic system.273... 

In a different approach three different structurally defined aza-crown ethers were treated with 10 different metal salts in a spatially addressable format in a 96-well microtiter plate, producing 40 catalysts, which were tested in the hydrolysis of /xnitrophenol esters.32 A plate reader was used to assess catalyst activity. A cobalt complex turned out to be the best catalyst. Higher diversity is potentially possible, but this would require an efficient synthetic strategy. This research was extended to include lanthanide-based catalysts in the hydrolysis of phospho-esters of DNA.33... 

Recently, rare-earth metal complexes have attracted considerable attention as initiators for the preparation of PLA via ROP of lactides, and promising results were reported in most cases [94—100]. Group 3 members (e.g. scandium, yttrium) and lanthanides such as lutetium, ytterbium, and samarium have been frequently used to develop catalysts for the ROP of lactide. The principal objectives of applying rare-earth complexes as initiators for the preparation of PLAs were to investigate (1) how the spectator ligands would affect the polymerization dynamics (i.e., reaction kinetics, polymer composition, etc.), and (2) the relative catalytic efficiency of lanthanide(II) and (III) towards ROPs. 

The LLB catalysts described above served an important role in demonstrating the proof of principle for catalysis with lanthanide-BINOL complexes. In addition, they were the first catalysts for the enantioselective nitroaldol reaction and gave respectable selectivities in synthetically useful yields. However, the reactions required at least 3.3 mol % of the catalysts for efficient conversion, and at that loading the reactions are rather slow. Clearly, the need for more effective catalysts is indicated. Consideration of the mechanism for the catalytic asymmetric... 

Shibasaki, M. and Groger, H. (1999) Chiral heterobimetallic lanthanoid complexes highly efficient multifunctional catalysts for the asymmetric formation of CC CO and CP bonds. Topics in Organometallic Chemistry, 2 (Lanthanides) 199-232. 

Half-sandwich lanthanide alkyl complexes and, subsequently oranolanthanide amides were found to be highly efficient catalysts for the cross-coupling reactions of carbodiimides with alkynes and amines, respectively [136, 137]. Although the half-sandwich lanthanide alkyl complexes can also catalyze the dimerization of alkynes, no homodimerization product is observed in the reaction of alkynes with carbodiimides. These reactions offer a wide scope for the substrates of terminal alkynes and amines, respectively [138]. 

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