Understanding the influence of donor-acceptor diazo compounds on the catalyst efficiency of B(C6F5)3 towards carbene formation

Babaahmadi, Rasool, Dasgupta, Ayan, Hyland, Christopher J. T., Yates, Brian F., Melen, Rebecca L. ORCID: https://orcid.org/0000-0003-3142-2831 and Ariafard, Alireza 2022. Understanding the influence of donor-acceptor diazo compounds on the catalyst efficiency of B(C6F5)3 towards carbene formation. Chemistry - A European Journal 28 (11) , e202104376. 10.1002/chem.202104376

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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(C6F5)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(C6F5)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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Additional Information:	This is an open access article under the terms of the Creative Commons Attribution License
Publisher:	Wiley
ISSN:	0947-6539
Funders:	EPSRC
Date of First Compliant Deposit:	27 January 2022
Date of Acceptance:	27 December 2021
Last Modified:	16 May 2023 20:13
URI:	https://orca.cardiff.ac.uk/id/eprint/147018

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