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Competition Between Cyclization and Unusual Norrish Type I and Type II Nitro-Acyl Migration Pathways in the Photouncaging of 1-Acyl-7-nitroindoline Revealed by Computations

preprint
revised on 22.09.2020 and posted on 23.09.2020 by Pierpaolo Morgante, Charitha Guruge, Yannick P. Ouedraogo, Nasri Nesnas, Roberto Peverati
The 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and acyl migration pathways, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which is reported here for the first time. We also introduced a computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.

Funding

National Science Foundation CNS 09-23050

National Institutes of Health R15-GM112119-01A1

History

Email Address of Submitting Author

rpeverati@fit.edu

Institution

Florida Institute of Technology

Country

USA

ORCID For Submitting Author

0000-0001-7774-9923

Declaration of Conflict of Interest

The Authors declare no conflict of interest

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