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

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posted on 2023-05-21, 07:40 authored by Rasool Babaahmadi, Dasgupta, A, Hyland, CJT, Brian YatesBrian Yates, Melen, RL, Alireza AriafardAlireza Ariafard

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.

Funding

Australian Research Council

University of Wollongong

History

Publication title

Chemistry - A European Journal

Volume

28

Issue

11

Article number

e202104376

Number

e202104376

Pagination

1-7

ISSN

0947-6539

Department/School

School of Natural Sciences

Publisher

Wiley-V C H Verlag Gmbh

Place of publication

Po Box 10 11 61, Weinheim, Germany, D-69451

Rights statement

2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution 4.0 International (CC BY 4.0) License, (https://creativecommons.org/licenses/by/4.0/) which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Repository Status

  • Open

Socio-economic Objectives

Expanding knowledge in the chemical sciences

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