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Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes.

ABSTRACT: Several new trivalent dinuclear rare earth 2,2'-methylenebis(6-tert-butyl-4-methylphenolate) (mbmp^2- ) complexes with the general form [Ln₂ (mbmp)₃ (thf)_n ] (Ln=Sm 1, Tb 2 (n=3), and Ho 3, Yb 4 (n=2), and a tetravalent cerium complex [Ce(mbmp)₂ (thf)₂ ] (5) have been synthesised by RTP (redox transmetallation/protolysis) reactions from lanthanoid metals, Hg(C₆ F₅ )₂ and the biphenol mbmpH₂ . These new complexes and some previously reported partially protonated rare earth biphenolate complexes [Ln(mbmp)(mbmpH)(thf)_n ] react with lithium, aluminium, potassium and zinc organometallic reagents to form lanthanoid-main group heterobimetallic species. When reaction mixtures containing the Ln biphenolate complexes were treated with n-butyllithium, both molecular ([Li(thf)₂ Ln(mbmp)₂ (thf)_n ] (Ln=La 6, Pr 7 (n=2) and Er 8, Yb 9, and Lu 10 (n=1)) and charge separated ([Li(thf)₄ ][Ln(mbmp)₂ (thf)₂ ] (Ln=Y 11, Sm 12, Dy 13, and Ho 14) complexes were isolated. Treatment with trimethylaluminium also led to isolation of molecular ([AlMe₂ Ln(mbmp)₂ (thf)₂ ] (Ln=Pr 15, Sm 16, and Tb 17)) and ionic [La(mbmp)(thf)₅ ][AlMe₂ (mbmp)] (18) complexes. One gadolinium-potassium ([K(thf)₃ Gd(mbmp)₂ (thf)₂ ] (19)), and one ytterbium-zinc species ([ZnEtYb(mbmp)₂ (thf)] (20)) were isolated from treatment of reaction mixtures with potassium bis(trimethylsilyl)amide and diethylzinc respectively.

SUBMITTER: Ali SH

PROVIDER: S-EPMC9303937 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of ?,?-unsaturated ketones can invoke more strategic C-C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with ?-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, ?-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous magnesium ProPhenol complex was used to facilitate enantioselective diazoacetate aldol reactions with aryl, ?,?-unsaturated, and aliphatic aldehydes. The utility of bimetallic ProPhenol catalysts was extended to asymmetric additions with a wide range of substrate combinations. Effective pronucleophiles include oxazolones, 2-furanone, nitroalkanes, pyrroles, 3-hydroxyoxindoles, alkynes, meso-1,3-diols, and dialkyl phosphine oxides. These substrates were found to be effective with a number of electrophiles, including aldehydes, imines, nitroalkenes, acyl silanes, vinyl benzoates, and ?,?-unsaturated carbonyls. A truly diverse range of enantioenriched compounds have been prepared using the ProPhenol ligand, and the commercial availability of both ligand enantiomers makes it ideally suited for the synthesis of complex molecules. To date, enantioselective ProPhenol-catalyzed reactions have been used in the synthesis of more than 20 natural products.

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Lanthanoid Biphenolates as a Rich Source of Lanthanoid-Main Group Heterobimetallic Complexes.

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