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

19 August 2020, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

photo-uncaging chemistry
photo-uncaging properties
photo-uncaging reaction
Density Functional Calculations
Mechanistic studies
Computational Organic Chemistry
Quantum Yield
Norrish Type II Photochemical Reaction
Norrish Type I Photochemical Reaction
Norrish type reactions
Unusual Transition State

Supplementary materials

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Description
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Title
DFT Uncaging SI CRXIV
Description
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