Anionic Conjugate Addition Oligomerization of Carbon Dioxide/Butadiene Derived Lactones

• Published in: ACS macro letters 2024-06, Vol.13 (6), p.658-663
• Main Authors: Crawford, Brennan J., Bochenek, Calum, Garcia Espinosa, Luis D., Keating, Addie R., Williams-Pavlantos, Kayla, Wesdemiotis, Chrys, Eagan, James M.
• Format: Article
• Language: English
• ISSN: 2161-1653; 2161-1653
• DOI: 10.1021/acsmacrolett.4c00164

Nucleophilic and non-nucleophilic bases have been employed in anionic oligomerization of unsaturated δ-valerolactone (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one) (1). Compared to the seminal findings with 1,5,7-triazabicyclo[4.4.0]­dec-5-ene (TBD), the unsaturated lactone reacts with guanidines, disilazanes, and phosphazenes both in bulk and in solution with higher productivities and activities, reaching full conversion with turnover frequencies up to 382 h–1. Additionally, reactions using phosphazenes and NaHMDS were active at 1 mol % catalyst loadings both in solvent and in bulk monomer at room temperature. Characterization of the reaction products by 1H, 13C, FTIR, MALDI-MS, tandem mass spectrometry (MS/MS), and ion mobility mass spectrometry (IM-MS) revealed microstructural differences dependent on the nucleophilicity of the organocatalytic base and reaction conditions. The products from phosphazene-catalyzed reactions are consistent with selective vinylogous 1,4-conjugate addition, whereas both conjugate addition and ring-opening mechanisms are observed in TBD. DSC reveals that these microstructures can be tuned to have a T g range between −18 and 80 °C, while SEC and MALDI-MS reveal that only low molar mass oligomers are formed (748–5949 g/mol). From these results, an approach for selectively favoring the vinylogous 1,4-conjugate addition pathway is obtained over ring-opening reactivity.