59995-49-2Relevant articles and documents
Chemoselective formation of cyclo-aliphatic and cyclo-olefinic 1,3-diolsviapressure hydrogenation of potentially biobased platform molecules using Kn?lker-type catalysts
Alsters, Paul L.,Chou, Khi Chhay,De Wildeman, Stefaan M. A.,Faber, Teresa,Hadavi, Darya,Han, Peiliang,Quaedflieg, Peter J. L. M.,Schwalb Freire, Alfonso J.,Verzijl, Gerard K. M.,van Slagmaat, Christian A. M. R.
supporting information, p. 10102 - 10112 (2021/08/03)
The hydrogenative conversions of the biobased platform molecules 4-hydroxycyclopent-2-enone and cyclopentane-1,3-dione to their corresponding 1,3-diols are established using a pre-activated Kn?lker-type iron catalyst. The catalyst exhibits a high selectivity for ketone reduction, and does not induce dehydration. Moreover, by using different substituents of the ligand, thecis-transratio of the products can be affected substantially. A decent compatibility of this catalytic system with various structurally related substrates is demonstrated.
Synthesis of agelastatin A and derivatives premised on a hidden symmetry element leading to analogs displaying anticancer activity
Bertonha, Ariane F.,Ho, Matthew,Ingros, Alec,Kim, Minwoo,Reisenauer, Keighley,Robinson, Joshua,Romo, Daniel,Svatek, Haleigh,Taube, Joseph,Xue, Haoran
supporting information, (2021/08/04)
Concise total syntheses of (±)-7-hydroxy debromo agelastatin A (AglA), (±)-AglA, and 11-nitro AglA are presented based on an identified pseudo-symmetry element. This synthetic strategy was developed based on a desire to improve solubility of this potent anticancer agent while also developing a synthetic strategy that would enable late-stage variation of the pyrrole moiety. A stability study of pyrrole-derived carbinolamines revealed critical substituent effects impacting the equilibrium between the cyclic carbinolamine and keto pyrrole forms. 7-Hydroxy AglA existed primarily in the ketopyrrole form however the des-bromo variant existed primarily in the cyclic carbinolamine form. Cytotoxicity assays revealed activity for a 13-nitro AglA derivative (～14–63 μM) for breast cancer cells (MDA-MB-231 and MCF7) and a glioblastoma cell line (U87) while for 7-hydroxy des-bromo AglA, measurable activity was only observed against the glioblastoma cell line.
Double-metal cyanide as an acid and hydrogenation catalyst for the highly selective ring-rearrangement of biomass-derived furfuryl alcohol to cyclopentenone compounds
Deng, Qiang,Deng, Shuguang,Gao, Rui,Li, Xiang,Lu, Chenxi,Tong, Zhikun,Wang, Jun,Yu, Lian,Zeng, Zheling,Zou, Ji-Jun
supporting information, p. 2549 - 2557 (2020/05/28)
Herein, novel green synthetic routes to 4-hydroxy-2-cyclopentenone (HCP) and 2-cyclopentenone (CPE) from biomass-derived furfuryl alcohol via double-metal cyanide catalysis are proposed. For the synthesis of HCP, in comparison to conventional solid acids (i.e., Amberlyst-15), MOFs with coordinatively unsaturated metal ions as pure Lewis acid sites exhibit advantageous catalytic selectivity in the reaction under an N2 atmosphere in a bi-phasic water/n-hexane solvent system. FeZn and FeZn-P result in an HCP yield of 77.4% and 88.2%, respectively. For the CPE synthesis, the reaction conditions are the same as those for HCP, except a mono-phasic water solvent system and H2 atmosphere were employed. In addition to the acid-catalyzed rearrangement reaction, FeZn-DMC exhibits catalytic hydrogenation capability via heterolytic cleavage of the H-H bond over Zn-N frustrated Lewis pairs, and a CPE yield of 61.5% is obtained. The DFT simulation indicates that the acid sites and catalytic acid sites are ascribed to the tri-coordinatively unsaturated Zn2+ site (Zn(N)3) on the catalyst surface. Moreover, the DMC catalyst shows excellent stability and recycling performance. This work not only provides an efficient and green catalytic system for CPE and HCP preparation but also demonstrates the interesting bifunctional catalysis of both acid and hydrogenation catalysis over DMC.
