Direct observation of o-benzyne formation in photochemical hexadehydro-Diels-Alder (hν-HDDA) reactions.

Chemical Science
Xiaonan MaTobias Brixner

Abstract

Reactive ortho-benzyne derivatives are believed to be the initial products of liquid-phase [4 + 2]-cycloadditions between a 1,3-diyne and an alkyne via what is known as a hexadehydro-Diels-Alder (HDDA) reaction. The UV/VIS spectroscopic observation of o-benzyne derivatives and their photochemical dynamics in solution, however, have not been reported previously. Herein, we report direct UV/VIS spectroscopic evidence for the existence of an o-benzyne in solution, and establish the dynamics of its formation in a photoinduced reaction. For this purpose, we investigated a bis-diyne compound using femtosecond transient absorption spectroscopy in the ultraviolet/visible region. In the first step, we observe excited-state isomerization on a sub-10 ps time scale. For identification of the o-benzyne species formed within 50-70 ps, and the corresponding photochemical hexadehydro-Diels-Alder (hν-HDDA) reactions, we employed two intermolecular trapping strategies. In the first case, the o-benzyne was trapped by a second bis-diyne, i.e., self-trapping. The self-trapping products were then identified in the transient absorption experiments by comparing their spectral features to those of the isolated products. In the second case, we used pery...Continue Reading

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Citations

Feb 7, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Ashok Kakkar
Mar 31, 2021·Chemistry : a European Journal·Jan Maier, Todd B Marder
Oct 20, 2021·Angewandte Chemie·Jesús Castro-EstebanDiego Peña

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Methods Mentioned

BETA
NMR
X-ray

Software Mentioned

R
package
TIMP
Gaussian
Glotaran
Multiwfn

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