Manganese—New prominent actor in transfer hydrogenation catalysis

Azouzi, Karim; Valyaev, Dmitry A.; Bastin, Stéphanie; Sortais, Jean‐Baptiste

doi:10.1016/j.cogsc.2021.100511

Cited by 36 publications

(28 citation statements)

References 38 publications

(44 reference statements)

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“…Indeed, there are some excellent reviews compiling all the reports on Mn-catalyzed hydrogenative and dehydrogenative transformations. 38,[43][44][45][46][47][49][50][51] However, most of these scattered reviews summarize the research development with minimal analysis of catalyst and reaction development and focus on a particular type of reaction instead of compiling them in a single place. (Scheme 1)…”

Section: Introductionmentioning

confidence: 99%

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

et al. 2022

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“…12 For instance, within the homogeneous catalysis area, molecularly defined Mn compounds have shown good to excellent results in dehydrogenative couplings, 13 hydroaminations, 14 hydrations, 15 N -alkylations, 16 alkyne functionalizations, 17 and (transfer) hydrogenations. 18…”

Section: Introductionmentioning

confidence: 99%

Manganese-catalyzed transfer semihydrogenation of internal alkynes to E-alkenes with iPrOH as hydrogen source

Torres-Calis

Garcı́a

2022

Catal. Sci. Technol.

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“…In these well‐defined coordinative environments of PNP and NNN pincer ligands, the Mn‐catalyst demonstrates a broad substrate scope and promising chemoselectivity even among various off‐site functional groups. This breakthrough was the starting point for enormous progress in this field in parallel with the extensive development of Mn‐catalyzed TH [8] . Phosphine‐free ligands are interesting to leverage Mn‐catalysts as a sustainable feedstock replacement for late transition metals because phosphine ligands are relatively expensive [9] .…”

Section: Introductionmentioning

confidence: 99%

“…This breakthrough was the starting point for enormous progress in this field in parallel with the extensive development of Mn-catalyzed TH. [8] Phosphine-free ligands are interesting to leverage Mn-catalysts as a sustainable feedstock replacement for late transition metals because phosphine ligands are relatively expensive. [9] The inclusion of stereogenic centers in the phosphine-free ligands have led to reported discoveries of ATH in ever-improving enantiomeric excess.…”

Section: Introductionmentioning

confidence: 99%

Aluminum‐Ligand Cooperative O−H Bond Activation Initiates Catalytic Transfer Hydrogenation

et al. 2022

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Molecular design ultimately furnishes improvements in performance over time, and this has been the case for Rh-and Irbased molecular catalysts currently used in transfer hydrogenation (TH) reactions for fine chemical synthesis. In this report, we describe a molecular pincer ligand Al catalyst for TH, (I 2 P 2À )Al(THF)Cl (I 2 P = diiminopyridine; THF = tetrahydrofuran). The mechanism for TH is initiated by two successive Al-ligand cooperative bond activations of the OÀ H bonds in two molecules of isopropanol ( i PrOH) to afford six-coordinate (H 2 I 2 P)Al(O i Pr) 2 Cl. Stoichiometric chemical reactions and kinetic experiments suggest an ordered transition state, supported by polar solvents, for concerted hydride transfer from i PrO À to substrate. Metal-ligand cooperative hydrogen bonding in a cyclic transition state is a likely support for the concerted hydride transfer event. The available data does not support involvement of an intermediate Al-hydride in the TH. Proof-ofprinciple reactions including the conversion of isopropanol and benzophenone to acetone and diphenylmethanol with 90 % conversion in 1 h are described. The analogous hydride compound, (I 2 P 2À )Al(THF)H, also cleaves the OÀ H bond in i PrOH to afford (HI 2 P À )Al(O i Pr)H and (HI 2 P À )Al(O i Pr) 2 , but no activity for catalytic TH was observed.

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Manganese—New prominent actor in transfer hydrogenation catalysis

Cited by 36 publications

References 38 publications

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Manganese-catalyzed transfer semihydrogenation of internal alkynes to E-alkenes with iPrOH as hydrogen source

Aluminum‐Ligand Cooperative O−H Bond Activation Initiates Catalytic Transfer Hydrogenation

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