Stereoselective synthesis of tetra- and tri-substituted alkenyl nitriles via aminative ring-opening of cyclopropenes with iron-aminyl radical
Year: 2025
Type: article
Abstract: The ring opening of cyclopropenes provides a compelling platform for the rapid synthesis of various polysubstituted acyclic alkenes. However, radical-mediated reactions of this type remain underexplored, and none of the existing methods have successfully produced tetrasubstituted olefins with high stereoselectivity. We present here an aminative ring-opening of cyclopropenes with iron-aminyl radical to afford tetrasubstituted alkenyl nitriles in a highly stereoselective manner. Computational studies indicate that both the substrate-directed radical addition and the following stereospecific ring-opening of cyclopropyl radical contribute to the extraordinary stereocontrol observed in the reaction. In addition, trisubstituted alkenyl nitriles could also be obtained using this method or via a base-promoted isomerization of the tetrasubstituted alkenyl nitriles, both with consistently high stereoselectivity. The ring opening of cyclopropenes provides a compelling platform for the rapid synthesis of various polysubstituted acyclic alkenes, but radical-mediated reactions of this type remain underexplored. Here, the authors report an aminative ring-opening of cyclopropenes with iron-aminyl radical to afford tetrasubstituted alkenyl nitriles.
Source: Nature Communications
Authors: Qian Wang, Jin-Kai Cheng, Shi-Xiong Tang, Kendall N. Houk, Fei Wang
Institutions: Nankai University, University of California, Los Angeles
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $6,990
OpenAlex ID: W4409147708