Organomanganese / amido-phosphine (DAPTA) catalyst for rapid cyanosilylation of aldehydes in glycerol and solvent-free conditions at room temperature

Abdallah G. Mahmoud; M. Fátima C.Guedes da Silva; Armando J.L. Pombeiro

doi:10.1016/j.cattod.2023.114056

Organomanganese / amido-phosphine (DAPTA) catalyst for rapid cyanosilylation of aldehydes in glycerol and solvent-free conditions at room temperature

Abdallah G. Mahmoud, M. Fátima C.Guedes da Silva, Armando J.L. Pombeiro

Faculty of Science & Engineering

Research output: Contribution to journal › Article › peer-review

Abstract

A mixture of the organomanganese precursor [Cp^Me-Mn(CO)₃] and the amido-phosphine 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) has been utilized in a highly efficient homogeneous catalytic process for the cyanosilylation of aromatic and aliphatic aldehydes in glycerol and under solvent-free conditions. A catalyst loading as low as 0.1 mol % led to a quantitative conversion of various aldehydes into the corresponding cyanohydrins in 15 min at room temperature. Multinuclear NMR and ESI(+)MS analysis revealed a mechanism conceivably evolving via a double activation process where DAPTA acts as a Lewis base and the in situ generated [Cp^Me-Mn(DAPTA)(CO)₂] organomanganese species as a Lewis acid.

Original language	English
Article number	114056
Journal	Catalysis Today
Volume	418
DOIs	https://doi.org/10.1016/j.cattod.2023.114056
Publication status	Published - 1 Jun 2023

Keywords

Cyanosilylation
DAPTA
Glycerol
Homogeneous catalysis
Organomanganese
P-ligand
Tetrel σ-hole bond

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10.1016/j.cattod.2023.114056

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@article{e0c171f9a5ba4e9583703ad1547b93ff,

title = "Organomanganese / amido-phosphine (DAPTA) catalyst for rapid cyanosilylation of aldehydes in glycerol and solvent-free conditions at room temperature",

abstract = "A mixture of the organomanganese precursor [CpMe-Mn(CO)3] and the amido-phosphine 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) has been utilized in a highly efficient homogeneous catalytic process for the cyanosilylation of aromatic and aliphatic aldehydes in glycerol and under solvent-free conditions. A catalyst loading as low as 0.1 mol \% led to a quantitative conversion of various aldehydes into the corresponding cyanohydrins in 15 min at room temperature. Multinuclear NMR and ESI(+)MS analysis revealed a mechanism conceivably evolving via a double activation process where DAPTA acts as a Lewis base and the in situ generated [CpMe-Mn(DAPTA)(CO)2] organomanganese species as a Lewis acid.",

keywords = "Cyanosilylation, DAPTA, Glycerol, Homogeneous catalysis, Organomanganese, P-ligand, Tetrel σ-hole bond",

author = "Mahmoud, \{Abdallah G.\} and \{da Silva\}, \{M. F{\'a}tima C.Guedes\} and Pombeiro, \{Armando J.L.\}",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors",

year = "2023",

month = jun,

day = "1",

doi = "10.1016/j.cattod.2023.114056",

language = "English",

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journal = "Catalysis Today",

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T1 - Organomanganese / amido-phosphine (DAPTA) catalyst for rapid cyanosilylation of aldehydes in glycerol and solvent-free conditions at room temperature

AU - Mahmoud, Abdallah G.

AU - da Silva, M. Fátima C.Guedes

AU - Pombeiro, Armando J.L.

PY - 2023/6/1

Y1 - 2023/6/1

N2 - A mixture of the organomanganese precursor [CpMe-Mn(CO)3] and the amido-phosphine 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) has been utilized in a highly efficient homogeneous catalytic process for the cyanosilylation of aromatic and aliphatic aldehydes in glycerol and under solvent-free conditions. A catalyst loading as low as 0.1 mol % led to a quantitative conversion of various aldehydes into the corresponding cyanohydrins in 15 min at room temperature. Multinuclear NMR and ESI(+)MS analysis revealed a mechanism conceivably evolving via a double activation process where DAPTA acts as a Lewis base and the in situ generated [CpMe-Mn(DAPTA)(CO)2] organomanganese species as a Lewis acid.

AB - A mixture of the organomanganese precursor [CpMe-Mn(CO)3] and the amido-phosphine 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) has been utilized in a highly efficient homogeneous catalytic process for the cyanosilylation of aromatic and aliphatic aldehydes in glycerol and under solvent-free conditions. A catalyst loading as low as 0.1 mol % led to a quantitative conversion of various aldehydes into the corresponding cyanohydrins in 15 min at room temperature. Multinuclear NMR and ESI(+)MS analysis revealed a mechanism conceivably evolving via a double activation process where DAPTA acts as a Lewis base and the in situ generated [CpMe-Mn(DAPTA)(CO)2] organomanganese species as a Lewis acid.

KW - Cyanosilylation

KW - DAPTA

KW - Glycerol

KW - Homogeneous catalysis

KW - Organomanganese

KW - P-ligand

KW - Tetrel σ-hole bond

UR - https://www.scopus.com/pages/publications/85150764326

U2 - 10.1016/j.cattod.2023.114056

DO - 10.1016/j.cattod.2023.114056

M3 - Article

AN - SCOPUS:85150764326

SN - 0920-5861

VL - 418

JO - Catalysis Today

JF - Catalysis Today

M1 - 114056

ER -

Organomanganese / amido-phosphine (DAPTA) catalyst for rapid cyanosilylation of aldehydes in glycerol and solvent-free conditions at room temperature

Abstract

Keywords

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