Fiorani Giulia, Stuck Moritz, Martín Carmen, Belmonte Marta Martínez, Martin Eddy, Escudero-Adán Eduardo C, Kleij Arjan W
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007, Tarragona, Spain.
Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010, Barcelona, Spain.
ChemSusChem. 2016 Jun 8;9(11):1304-11. doi: 10.1002/cssc.201600238. Epub 2016 May 9.
The challenging coupling of highly substituted terpene oxides and carbon dioxide into bio-based cyclic organic carbonates catalyzed by Al(aminotriphenolate) complexes is reported. Both acyclic as well as cyclic terpene oxides were used as coupling partners, showing distinct reactivity/selectivity behavior. Whereas cyclic terpene oxides showed excellent chemoselectivity towards the organic carbonate product, acyclic substrates exhibited poorer selectivities owing to concomitant epoxide rearrangement reactions and the formation of undesired oligo/polyether side products. Considering the challenging nature of these coupling reactions, the isolated yields of the targeted bio-carbonates are reasonable and in most cases in the range 50-60 %. The first crystal structures of tri-substituted terpene based cyclic carbonates are reported and their stereoconnectivity suggests that their formation proceeds through a double inversion pathway.
报道了由铝（氨基三酚盐）配合物催化的高取代萜烯氧化物与二氧化碳具有挑战性的偶联反应，生成生物基环状有机碳酸酯。无环和环状萜烯氧化物均用作偶联伙伴，表现出不同的反应性/选择性行为。环状萜烯氧化物对有机碳酸酯产物表现出优异的化学选择性，而无环底物由于伴随的环氧化物重排反应和不期望的低聚/聚醚副产物的形成而表现出较差的选择性。考虑到这些偶联反应的挑战性，目标生物碳酸酯的分离产率是合理的，在大多数情况下在50%-60%的范围内。报道了三取代萜烯基环状碳酸酯的首个晶体结构，其立体连接性表明它们的形成是通过双反转途径进行的。
