N,N,O-Tridentate Mixed Lithium–Magnesium and Lithium–Aluminum Complexes: Synthesis, Characterization, and Catalytic Activities

Hua, Yupeng; Han, Hyounkoo; Wei, Xuehong

doi:10.1021/acs.organomet.6b00921

Cited by 14 publications

(7 citation statements)

References 76 publications

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“…For example, using benzaldehyde and dry isopropyl alcohol as a model reaction with 5 mol % of catalyst in toluene, the benzyl alcohol product was formed in yields of 87.6% and 52.7%, respectively (Scheme ). Using 90 a range of carbonyl compounds (six aldehydes and two ketones) were then selectively converted to the corresponding alcohols in yields ranging from 62.4 to 93.8% . Further information is provided in the aluminum section .…”

Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

“…An interesting lithium aluminate complex was prepared by the deprotonation of the alcohol HOC(CH 2 ) 5 CH 2 N(Me)CH 2 CH 2 NMe 2 (HOR′) with RAlMe 2 (R = Me, Cl) followed by cocomplexation with n BuLi (R = Me) or cocomplexation/salt metathesis with two equivalents of n BuLi (R = Cl) to give LiAl(OR′)(Me) x ( n Bu) 3‑ x (R = Me, x = 2, 222 ; R = Cl, x = 1, 223 ) . The presence of the N(Me)CH 2 CH 2 NMe 2 arm provided an intramolecular Lewis basic solvating source akin to TMEDA (note the alcohol was originally prepared by deprotonating a TMEDA arm and adding this across the ketone functionality of cyclohexanone), but this was not sufficient to provide access to discrete molecular bimetallic species, with polymerization occurring via CH 3 bridges.…”

Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

“…Using 90 a range of carbonyl compounds (six aldehydes and two ketones) were then selectively converted to the corresponding alcohols in yields ranging from 62.4 to 93.8%. 91 Further information is provided in the aluminum section 2.5.4.…”

Section: Chemical Reviewsmentioning

confidence: 99%

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Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

2019

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The development of synthetic chemistry since the early 1900s owes much to the service of organolithium reagents. Brilliant bases (e.g., deprotonating C−H bonds), nucleophiles (e.g., adding to unsaturated molecules), and transfer agents (e.g., delivering ligands to other metals), these versatile virtuosi and to a lesser extent the organic derivatives of the other common alkali metals sodium and potassium have proved indispensable in both academia and technology. Today these monometallic compounds are still utilized widely in synthetic campaigns, but in recent years they have been joined by an assortment of bimetallic formulations that also contain an alkali metal but in company with another metal. These bimetallic formulations often exhibit unique chemistry that can be interpreted in terms of synergistic effects, for which the alkali metal is essential, though it is often the second metal that performs the synthetic transformation. Here, this "alkali-metal-mediated" chemistry is surveyed focusing mainly on bimetallic formulations containing two alkali metals or an alkali metal paired with magnesium, calcium, zinc, aluminum, or gallium. In this International Year of the Periodic Table (IYPT), we ponder whether a Pairiodic Table of Element Pairs will emerge in the future.

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Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

Section: Heterometallic Synergistic Main Group Complexesmentioning

confidence: 99%

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Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

2019

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“…These products were characterized by single crystal X-ray diffraction experiments as [(py)(OR) 2 Ti(κ 2 (O,μ-O′)(OC 6 H 4– x (CH 2 O)-2)(L) x ] (OR = OPr i , x = 1, L = H ( 1a ), OMe-3 ( 2a ), Br-5 ( 3a ·py), NO 2 -5 ( 4a ·4py), x = 2, Bu t -3,5 ( 5a ), I-3,5 ( 6a ); OR = ONep, x = 1, L = H ( 1b ), OMe-3 ( 2b ), Br-5 ( 3b ·py), NO 2 -5 ( 4b ), x = 2, Bu t -3,5 ( 5b ), I-3,5 ( 6b ·py)). Elucidation of the potential mechanism for this process on the basis the above reactivity was found to be consistent with a Meerwein–Pondorf–Verley (MPV)-like reduction pathway. − The synthesis, characterization, and attempts to elucidate the reduction pathway of this unprecedented aldehyde reduction by a simple [M(OR) 4 ] is presented.…”

Section: Introductionmentioning

confidence: 86%

Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

et al. 2019

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A series of titanium alkoxides ([Ti(OR) 4 ] (OR = OCH(CH 3 ) 2 (OPr i ), OC(CH 3 ) 3 (OBu t ), and OCH 2 C(CH 3 ) 3 (ONep)) were modified with a set of substituted hydroxyl-benzaldehydes [HO-BzA-L x : x = 1, 2-hydroxybenzaldehyde (L = H), 2-hydroxy-3-methoxybenzaldehyde (OMe-3), 5-bromo-2-hydroxybenzaldehyde (Br-5), 2-hydroxy-5-nitrobenzaldehyde (NO 2 -5); x = 2, 3,5-di-tert-butyl-2-hydroxybenzaldehyde (Bu t -3,5), 2-hydroxy-3,5-diiodobenzaldehyde (I-3,5)] in pyridine (py). Instead of the expected simple substitution, each of the HO-BzA-L x modifiers were reduced to their respective diol [(py , NO 2 -5 (4a•4py); x = 2, Bu t -3,5 (5a), I-3,5 (6a), ONep; x = 1, L = H (1b), OMe-3 (2b), Br-5 (3b•py), NO 2 -5 (4b); x = 2, Bu t -3,5 (5b), I-3,5 (6b•py)), as identified by single crystal X-ray studies. The 1 H NMR spectral data were complex at room temperature but simplified at high temperatures (70 °C). Diffusion ordered spectroscopy (DOSY) NMR experiments indicated that 2a maintained the dinuclear structure in a solution independent of the temperature, whereas 2b appears to be monomeric over the same temperature range. On the basis of additional NMR studies, the mechanism of the reduction of the HO-BzA-L x to the dioxide ligand was thought to occur by a Meerwein−Pondorf−Verley (MPV) mechanism. The structures of 1a−6b appear to be the intermediate dioxide products of the MPV reduction, which became "trapped" by the Lewis basic solvate.

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“…They are also active catalysts for the polymerization of polar alkenes [26,27,28,29]. More recently, their activity in catalytic processes such as the hydroboration process [30] or Meerwein-Ponndorf-Verley (MPV) reactions [31] has also been described.…”

Section: Introductionmentioning

confidence: 99%

Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization

et al. 2018

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New heterometallic aluminium-alkali metal compounds have been prepared using Schiff bases with electron withdrawing substituents as ligands. The synthesis of these new species was achieved via the reaction of AlMe3 with the freshly prepared alkali-metallated ligand. The derivatives formed were characterized by NMR in solution and by single crystal X-ray diffraction in the solid state. Aluminate derivatives with lithium and sodium were prepared and a clear influence of the alkali metal in the final outcome is observed. The presence of a Na···F interaction in the solid state has a stabilization effect and the species [NaAlMe3L]2 can de isolated for the first time, which was not possible when using Schiff bases without electron withdrawing substituents as ligands.

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N,N,O-Tridentate Mixed Lithium–Magnesium and Lithium–Aluminum Complexes: Synthesis, Characterization, and Catalytic Activities

Cited by 14 publications

References 76 publications

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry

Trapped Intermediate of a Meerwein–Pondorf–Verley Reduction of Hydroxy Benzaldehyde to a Dialkoxide by Titanium Alkoxides

Aluminates with Fluorinated Schiff Bases: Influence of the Alkali Metal–Fluorine Interactions in Structure Stabilization

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