Synthesis and Characterization of Cyanobutadiene Isomers—Molecules of Astrochemical Significance
2020
Kougias, Samuel M. | Knezz, Stephanie N. | Owen, Andrew N. | Sanchez, Rodrigo A. | Hyland, Grace E. | Lee, Daniel J. | Patel, Aatmik R. | Esselman, Brian J. | Woods, R Claude | McMahon, Robert J.
Four cyanobutadiene isomers of considerable interest to the organic chemistry, molecular spectroscopy, and astrochemistry communities were synthesized in good yields and isolated as pure compounds: (E)-1-cyano-1,3-butadiene (E-1), (Z)-1-cyano-1,3-butadiene (Z-1), 4-cyano-1,2-butadiene (2), and 2-cyano-1,3-butadiene (3). A diastereoselective synthesis was developed to generate (E)-1-cyano-1,3-butadiene (1) (10:1 E/Z) via tandem SN2 and E2′ reactions. The potential energy surfaces of the E2′ reactions leading to (E)- and (Z)-1-cyano-1,3-butadiene (1) were analyzed by density functional theory calculations, and the observed diastereoselectivity was rationalized in the context of the Curtin–Hammett principle. The preparation of pure samples of these reactive compounds enables measurement of their laboratory rotational spectra, which are the critical data needed to search for these species in space by radioastronomy.
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