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Updated: Jun 22, 2025

Hydrolysis of a Ni-Schiff-Base Complex Using Conditions Suitable for Retention of Acid-labile Protecting Groups
Published on: April 6, 2017
Development and characterization of amino donor-acceptor Stenhouse adducts
Cesar A Reyes1, Hye Joon Lee1, Connie Karanovic1
1Department of Chemistry, Loker Hydrocarbon Research Institute, University of Southern California, 837 Bloom Walk, Los Angeles, CA, USA.
Abstract:
Donor-acceptor Stenhouse adducts (DASAs) are molecular photoswitches spurring wide interest because of their dynamic photophysical properties, complex photoswitching mechanism, and diverse applications. Despite breakthroughs in modularity for the donor, acceptor, and triene compartments, the backbone heteroatom remains static due to synthetic challenges. We provide a predictive tool and sought-after strategy to vary the heteroatom, introduce amino DASA photoswitches, and analyze backbone heteroatom effects on photophysical properties. Amino DASA synthesis is enabled by aza-Piancatelli rearrangements on pyrrole substrates, imparting an aromaticity-breaking rearrangement that capitalizes on nitrogen's additional bonding orbital and the inductive properties of sulfonyl groups. Amino DASA structure is confirmed by single crystal X-ray diffraction, the photochromic properties are characterized, and the photoswitch isomerization is investigated. Overall, the discovered pyrrole rearrangement enables the study of the DASA backbone heteroatom compartment and furthers our insight into the structure-property relationship of this complex photoswitch.
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The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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