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Understanding the Influence of Donor-Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6 F5)3 Towards Carbene Formation.
Chemistry. 2022 Feb 19; 28(11):e202104376.C

Abstract

Diazo compounds have been largely used as carbene precursors for carbene transfer reactions in a variety of functionalization reactions. However, the ease of carbene generation from the corresponding diazo compounds depends upon the electron donating/withdrawing substituents either side of the diazo functionality. These groups strongly impact the ease of N2 release. Recently, tris(pentafluorophenyl)borane [B(C6 F5)3 ] has been shown to be an alternative transition metal-free catalyst for carbene transfer reactions. Herein, a density functional theory (DFT) study on the generation of carbene species from α-aryl α-diazocarbonyl compounds using catalytic amounts of B(C6 F5)3 is reported. The significant finding is that the efficiency of the catalyst depends directly on the nature of the substituents on both the aryl ring and the carbonyl group of the substrate. In some cases, the boron catalyst has negligible effect on the ease of the carbene formation, while in other cases there is a dramatic reduction in the activation energy of the reaction. This direct dependence is not commonly observed in catalysis and this finding opens the way for intelligent design of this and other similar catalytic reactions.

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Authors+Show Affiliations

Babaahmadi R
School of Natural Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania, 7001, Australia.
Dasgupta A
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, Cymru/Wales, UK.
Hyland CJT
School of Chemistry and Molecular Bioscience, Molecular Horizons Research Institute, University of Wollongong, Wollongong, New South Wales, 2522, Australia.
Yates BF
School of Natural Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania, 7001, Australia.
Melen RL
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, Cymru/Wales, UK.
Ariafard A
School of Natural Sciences (Chemistry), University of Tasmania, Private Bag 75, Hobart, Tasmania, 7001, Australia.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

34958698

Citation

Babaahmadi, Rasool, et al. "Understanding the Influence of Donor-Acceptor Diazo Compounds On the Catalyst Efficiency of B(C6 F5)3 Towards Carbene Formation." Chemistry (Weinheim an Der Bergstrasse, Germany), vol. 28, no. 11, 2022, pp. e202104376.
Babaahmadi R, Dasgupta A, Hyland CJT, et al. Understanding the Influence of Donor-Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6 F5)3 Towards Carbene Formation. Chemistry. 2022;28(11):e202104376.
Babaahmadi, R., Dasgupta, A., Hyland, C. J. T., Yates, B. F., Melen, R. L., & Ariafard, A. (2022). Understanding the Influence of Donor-Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6 F5)3 Towards Carbene Formation. Chemistry (Weinheim an Der Bergstrasse, Germany), 28(11), e202104376. https://doi.org/10.1002/chem.202104376
Babaahmadi R, et al. Understanding the Influence of Donor-Acceptor Diazo Compounds On the Catalyst Efficiency of B(C6 F5)3 Towards Carbene Formation. Chemistry. 2022 Feb 19;28(11):e202104376. PubMed PMID: 34958698.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Understanding the Influence of Donor-Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6 F5)3 Towards Carbene Formation. AU - Babaahmadi,Rasool, AU - Dasgupta,Ayan, AU - Hyland,Christopher J T, AU - Yates,Brian F, AU - Melen,Rebecca L, AU - Ariafard,Alireza, Y1 - 2022/01/27/ PY - 2021/12/07/received PY - 2021/12/28/pubmed PY - 2021/12/28/medline PY - 2021/12/27/entrez KW - Lewis acid catalysis KW - carbene KW - density functional theory (DFT) KW - diazo compounds KW - mechanistic study KW - tris(pentafluorophenyl)borane SP - e202104376 EP - e202104376 JF - Chemistry (Weinheim an der Bergstrasse, Germany) JO - Chemistry VL - 28 IS - 11 N2 - Diazo compounds have been largely used as carbene precursors for carbene transfer reactions in a variety of functionalization reactions. However, the ease of carbene generation from the corresponding diazo compounds depends upon the electron donating/withdrawing substituents either side of the diazo functionality. These groups strongly impact the ease of N2 release. Recently, tris(pentafluorophenyl)borane [B(C6 F5)3 ] has been shown to be an alternative transition metal-free catalyst for carbene transfer reactions. Herein, a density functional theory (DFT) study on the generation of carbene species from α-aryl α-diazocarbonyl compounds using catalytic amounts of B(C6 F5)3 is reported. The significant finding is that the efficiency of the catalyst depends directly on the nature of the substituents on both the aryl ring and the carbonyl group of the substrate. In some cases, the boron catalyst has negligible effect on the ease of the carbene formation, while in other cases there is a dramatic reduction in the activation energy of the reaction. This direct dependence is not commonly observed in catalysis and this finding opens the way for intelligent design of this and other similar catalytic reactions. SN - 1521-3765 UR - https://www.unboundmedicine.com/medline/citation/34958698/Understanding_the_Influence_of_Donor_Acceptor_Diazo_Compounds_on_the_Catalyst_Efficiency_of_B_C6_F5_3_Towards_Carbene_Formation_ DB - PRIME DP - Unbound Medicine ER -