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Two‐step Conformational Control of a Dibenzo Diazacyclooctane Derivative by Stepwise Protonation
Author(s) -
Ishiwari Fumitaka,
Miyake Sayuri,
Inoue Keiki,
Hirose Keiji,
Fukushima Takanori,
Saeki Akinori
Publication year - 2021
Publication title -
asian journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.846
H-Index - 44
eISSN - 2193-5815
pISSN - 2193-5807
DOI - 10.1002/ajoc.202100154
Subject(s) - chemistry , protonation , derivative (finance) , supramolecular chemistry , stereochemistry , crystallography , crystal structure , ring (chemistry) , organic chemistry , ion , financial economics , economics
Abstract The conformational control of a dibenzo‐1,5‐diazacyclooctane (DACO) derivative with tertiary and secondary amino groups by stepwise protonation is investigated by single crystal X‐ray diffraction analysis, computational simulation, and variable temperature NMR measurements. The DACO derivative undergoes two‐step protonation, to afford bent‐shape monoprotonated and diprotonated species, whose conformations are different from each other. The monoprotonated form is characterized by a Tröger's‐base‐like proton‐bridged pseudo bicyclic structure, while the diprotonated form features a deformed boat‐shape eight membered ring structure. The degree of bending and conformational rigidity of the DACO skeleton become higher as the degree of the protonation is increased. Such a multistep conformational control of the DACO derivative would be useful for developing new stimuli‐responsive supramolecular systems that exhibit a multistep change in properties.