53716-82-8Relevant articles and documents
Levoglucosenone-derived precursors for the stereoselective synthesis of methylene-expanded analogues of C-nucleosides
Brel, Valery K.,Samet, Aleksandr V.,Konyushkin, Leonid D.,Stash, Adam I.,Belsky, Vitaly K.,Semenov, Victor V.
, p. 44 - 46 (2015)
Simple chiral precursors for the preparation of methylene-expanded C-nucleosides were developed, using as key steps pyrolysis of cellulose to levoglucosenone followed by hydrogenation and introduction of vinyl and ethynyl fragments to the 2-position.
Enzymatic reduction of levoglucosenone by an alkene reductase (OYE 2.6): A sustainable metal- and dihydrogen-free access to the bio-based solvent Cyrene
Mouterde, Louis M. M.,Allais, Florent,Stewart, Jon D.
, p. 5528 - 5532 (2018)
Levoglucosenone (LGO) has been successfully converted into the green polar aprotic solvent 2H-LGO (aka Cyrene) through an enzymatic process involving alkene reductases: wild-type Old Yellow Enzyme 2.6 (OYE 2.6 wt.) from Pichia stipitis and its mutant (OYE 2.6 Tyr78Trp) present the best conversion rates. This enzymatic process has been optimized in order to avoid the formation of the side-product (1R,2S)-2-hydroxy-6,8-dioxabicyclo[3.2.1]octan-4-one (OH-LGO) and reach total conversion (99%). Cyrene was then successfully isolated by continuous extraction in quantitative yield (99%).
Stereochemical aspects of the Beckman rearrangement of oximes of levoglucosenone and its dihydro derivative. Enantioselective synthesis of (+)-γ-pelargonolactone
Valeev,Gorobets,Tsypysheva,Singizova,Kalimullina,Safarov,Shitikova,Miftakhov
, p. 563 - 568 (2003)
Regiospecific C5-halogenation with retention of configuration occurred upon Beckman fragmentation of levoglucosenone oxime using SOCl 2 or PBr3. On the other hand, the oxime of its dihydro derivative gave under these conditions the C6-substitution product. A stereoselective synthetic scheme for (+)-γ-pelargonolactone, an attractant for the rice and corn weevils Sitophiltus zeamais, was developed from the fragmentation product of levoglucosenone oxime.
Preparation of the diastereomerically pure 2S-hydroxy derivative of dihydrolevoglucosenone (cyrene)
Sharipov, Bulat T.,Davydova, Anna N.,Faizullina, Liliya Kh.,Valeev, Farid A.
, p. 200 - 202 (2019/04/25)
Diastereomerically pure levoglucosenone alcohol, synthesized from levoglucosenone, upon hydrogenation on Raney Ni or Pd/BaSO4 undergoes epimerization at C2 atom caused by formation of cyrene by-product and its subsequent non-specific
Tuning zirconia-supported metal catalysts for selective one-step hydrogenation of levoglucosenone
Mazarío, Jaime,Parre?o Romero, Miriam,Concepción, Patricia,Chávez-Sifontes, Marvin,Spanevello, Rolando A.,Comba, María B.,Suárez, Alejandra G.,Domine, Marcelo E.
, p. 4769 - 4785 (2019/09/09)
Levoglucosenone, directly produced from cellulose-containing residual biomass via pyrolysis treatments, is believed to be a promising bio-renewable platform for both fine and commodity chemicals. In this work, the possibilities given by tuneable catalysts based on Pd and Pt supported on metallic oxides to produce the desired product in the one-pot hydrogenation of levoglucosenone are evaluated. Particularly, the excellent catalytic performance of Pd/ZrO2 and Pt/ZrO2 type materials for the synthesis of dihydrolevoglucosenone (or Cyrene) and levoglucosanol, respectively, during the mild hydrogenation of levoglucosenone is demonstrated. In the Cyrene synthesis, the Pd/t-ZrO2 material showed the best catalytic activity compared to other Pd-supported on metallic oxides. This catalyst achieved nearly 95% yields of Cyrene by working under mild reaction conditions, with very low catalyst loadings (≈3 wt%) and using water as the solvent. On the other hand, the one-pot hydrogenation of levoglucosenone to levoglucosanol is reported for the first time with a Pt-based heterogeneous catalyst (Pt/ZrO2-mix, yield ≈90%), by working at low temperatures and mild H2 pressures with water as the solvent. Comparison of the results attained with other Pt-supported metallic oxides let us to conclude that the metal crystal facets (specifically the 100 facet) play an important role in the hydrogenation process to give levoglucosanol selectively. In addition, the stability and re-usability of both catalysts under operational conditions are also evaluated. Finally, catalytic tests including the use of crude bio-liquids obtained from cellulose-rich biomass pyrolysis and containing ≈66 wt% of levoglucosenone are also assayed, thus demonstrating the possibility of scaling-up the process over these metals supported on zirconia catalysts.
