Lutz Marius D R, Kracht Felix, Marumoto Kota, Nozaki Kyoko
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, 113-8656, Japan.
Nat Commun. 2025 Aug 28;16(1):7326. doi: 10.1038/s41467-025-62409-2.
Carbon dioxide (CO) is an ideal chemical feedstock due to its abundance, low cost, low toxicity and its role as a greenhouse gas. Telomerization with butadiene give rise to functional small molecules and polymers with significant CO content, but the fossil origin of the olefin offsets sustainability benefits. Here, we present a palladium-catalyzed telomerization of CO with isoprene, two of the most prevalent organic compounds in the atmosphere, yielding "COOIL", an ideally 100% renewable δ-lactone containing 24 wt% CO, with high selectivity and turnover numbers above 100. A combination of a Pd catalyst, acetate, and controlled water promoted selectivity and conversion. Density functional theory calculations reveal reductive elimination as the rate-limiting and selectivity-determining step, preceded by isoprene dimerization. The head-tail pathway is the kinetic pathway while the tail-tail product is the thermodynamic product. This functionalized lactone also shows promise for polymerization under Lewis acid-promoted conditions, opening avenues for sustainable polymers from CO and bio-derived feedstocks.
二氧化碳（CO₂）因其储量丰富、成本低廉、毒性较低以及作为温室气体的作用，是一种理想的化学原料。与丁二烯进行端粒化反应可生成具有显著CO₂含量的功能性小分子和聚合物，但烯烃的化石来源抵消了可持续性优势。在此，我们展示了钯催化的CO₂与异戊二烯的端粒化反应，异戊二烯是大气中两种最普遍的有机化合物，生成了“CO₂油”，这是一种理想的100%可再生的δ-内酯，含有24 wt%的CO₂，具有高选择性且周转数高于100。钯催化剂、乙酸盐和受控水的组合促进了选择性和转化率。密度泛函理论计算表明，还原消除是限速和选择性决定步骤，在此之前是异戊二烯二聚化。头-尾途径是动力学途径，而尾-尾产物是热力学产物。这种功能化内酯在路易斯酸促进的条件下也显示出聚合的潜力，为来自CO₂和生物衍生原料的可持续聚合物开辟了道路。
