85354-35-4Relevant articles and documents
Chiral porous poly(ionic liquid)s: Facile one-pot, one-step synthesis and efficient heterogeneous catalysts for asymmetric epoxidation of olefins
Tian, Yabing,Wang, Jixia,Zhang, Shiguo,Zhang, Yan
, (2022/01/26)
Ionic liquids are potential media/solvents for asymmetric synthesis when combined with chiral catalysts, while most reported catalysts are homogenous, making them difficult to separate from the reaction systems. Herein, chiral porous poly(ionic liquid)s (
Enhanced enantioselectivity in heterogeneous manganese-catalyzed asymmetric epoxidation with nanosheets modified amino acid Schiff bases as ligands by modulating the orientation and the arrangement order
An, Zhe,Han, Hongbo,He, Jing,Jiang, Yitao,Ping, Qi,Shu, Xin,Song, Hongyan,Tang, Yuanzhong,Wang, Wenlong,Xiang, Xu,Zhu, Yanru
, p. 22 - 36 (2021/08/25)
Catalytic enantioselective epoxidation of olefins plays an important role in the production of optically-active epoxy. Transition-metal complexes prove efficient for the catalytic epoxidation of un-functionalized olefins by employing privileged chiral lig
Asymmetric azidohydroxylation of styrene derivatives mediated by a biomimetic styrene monooxygenase enzymatic cascade
Franssen, Maurice C. R.,Hollmann, Frank,Martínez-Montero, Lía,Paul, Caroline E.,Süss, Philipp,Schallmey, Anett,Tischler, Dirk
, p. 5077 - 5085 (2021/08/16)
Enantioenriched azido alcohols are precursors for valuable chiral aziridines and 1,2-amino alcohols, however their chiral substituted analogues are difficult to access. We established a cascade for the asymmetric azidohydroxylation of styrene derivatives leading to chiral substituted 1,2-azido alcohols via enzymatic asymmetric epoxidation, followed by regioselective azidolysis, affording the azido alcohols with up to two contiguous stereogenic centers. A newly isolated two-component flavoprotein styrene monooxygenase StyA proved to be highly selective for epoxidation with a nicotinamide coenzyme biomimetic as a practical reductant. Coupled with azide as a nucleophile for regioselective ring opening, this chemo-enzymatic cascade produced highly enantioenriched aromatic α-azido alcohols with up to >99% conversion. A bi-enzymatic counterpart with halohydrin dehalogenase-catalyzed azidolysis afforded the alternative β-azido alcohol isomers with up to 94% diastereomeric excess. We anticipate our biocatalytic cascade to be a starting point for more practical production of these chiral compounds with two-component flavoprotein monooxygenases.
Immobilization of (tartrate-salen)Mn(III) polymer complexes into SBA-15 for catalytic asymmetric epoxidation of alkenes
Jia, Yihong,ALOthman, Zeid A.,Liang, Rui,Cha, Shuangshuang,Li, Xiaoyong,Ouyang, Weiyi,Zheng, Aqun,Osman, Sameh M.,Luque, Rafael,Sun, Yang
, (2020/08/19)
A series of (tartrate-salen)Mn(III) polymer complexes were prepared and immobilized into SBA-15, being subsequently employed as catalysts in the asymmetric epoxidation of alkenes. 1H NMR, FT-IR, UV–vis, elemental analysis, GPC and ICP-AES demonstrated the successful synthesis of polymer complexes, while powdered XRD, nitrogen physisorption and XPS studies proved the immobilization of polymer complexes into SBA-15. Both homogeneous and heterogeneous catalysis revealed that configurations of major epoxide products were still determined by salen chirality but e.e. values could be improved when tartrate and salen were configurationally identical. Combinations of (R,R)-salen with (R,R)-tartrate usually offered higher enantioselectivities. SBA-15 was satisfactory supporting material due to the high enantioselectivities and recycling yields obtained. The synthesized SBA-15-supported (tartrate-salen)Mn(III) catalysts showed continuous high enantioselectivities for epoxidation of α-methylstyrene, indicating great prospects for large-scale production.
Visible-Light-Driven N-Heterocyclic Carbene Catalyzed γ- and ?-Alkylation with Alkyl Radicals
Dai, Lei,Xia, Zi-Hao,Gao, Yuan-Yuan,Gao, Zhong-Hua,Ye, Song
supporting information, p. 18124 - 18130 (2019/11/13)
The merging of photoredox catalysis and N-heterocyclic carbene (NHC) catalysis for γ- and ?-alkylation of enals with alkyl radicals was developed. The alkylation reaction of γ-oxidized enals with alkyl halides worked well for the synthesis γ-multisubstituted-α,β-unsaturated esters, including those with challenging vicinal all-carbon quaternary centers. The synthesis of ?-multisubstituted-α,β-γ,δ-diunsaturated esters by an unprecedented NHC-catalyzed ?-functionalization was also established.
Asymmetric epoxidation of unfunctionalized olefins with C2-symmetrical diphenol-derived axially coordinated homogeneous chiral bi-Mn(III) salen complexes
Dong, Tianyi,Wu, Xiaoju,Cai, Jiali,Huang, Jing
, p. 57 - 61 (2019/01/19)
A novel type of C2-symmetrical diphenol-derived and axially coordinated homogeneous chiral bi-Mn(III) salen complexes are synthesized and their catalytic effects in asymmetric epoxidation of unfunctionalized olefins are investigated in details. The results show that excellent enantioselectivities and high activities are achieved (enantioselectivities up to >99% in 99.9%) in the absence of expensive NMO. Compared with Jacobsen's catalyst, the configuration of C2-symmetrical homogeneous chiral bi-Mn(III) salen complex contribute to the catalytic reactivity and stability. Furthermore, these new homogeneous catalysts could be easily recovered and reused for 5 cycles without significant loss of their properties.
Computationally guided design of a readily assembled phosphite-thioether ligand for a broad range of pd-catalyzed asymmetric allylic substitutions
Biosca, Maria,Margalef, Jèssica,Caldentey, Xisco,Besora, Maria,Rodríguez-Escrich, Carles,Saltó, Joan,Cambeiro, Xacobe C.,Maseras, Feliu,Pàmies, Oscar,Diéguez, Montserrat,Pericàs, Miquel A.
, p. 3587 - 3601 (2018/04/14)
A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson-Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures.
Collaborative effect of Mn-porphyrin and mesoporous SBA-15 in the enantioselective epoxidation of olefins with oxygen
Berijani, Kayhaneh,Hosseini-Monfared, Hassan
, p. 113 - 120 (2017/11/10)
The rational design of heterogeneous, low cost transition metal complexes that can catalyze olefin with high enantioselectivity and activity has been a challenging goal for the synthetic chemist. In this study a chiral ion pair strategy was used for the synthesis of a biomimetic efficient manganese-tetrapyridylporphyrin (H2TPyP) catalyst for the asymmetric epoxidation of olefins with O2. Complex Mn-TPyP was covalently linked to mesoporous SBA-15 in heme-type environments and its counter ion was replaced by L-tartrate anion (SBA15-[Mn(TPyP)TA]). Chiral and achiral homogeneous analogous of Mn-TPyP were also prepared. The Mn-porphyrin confined in nanoreactors of SBA-15 exhibited enhanced activity (TOF = 652 h?1) and enantiomeric excess (ee 93%) compared with the value obtained when the same chiral catalyst functioned in homogeneous solution (TOF 97 h?1 and ee 83%) in the oxidation of 1-decene with O2/isobutyraldehyde. The high specific surface area, uniformly sized pore channels and site isolated active centers of the catalyst may contribute to the high activity and enantioselectivity. SBA15-[Mn(TPyP)TA] was structurally stable and could be recycled for repeated use. Total turnover number in the oxidation of styrene after five cycles was 47,400 with 86% epoxide selectivity and ee 86%.
Chiral Manganese Aminopyridine Complexes: the Versatile Catalysts of Chemo- and Stereoselective Oxidations with H2O2
Ottenbacher, Roman V.,Talsi, Evgenii P.,Bryliakov, Konstantin P.
, p. 78 - 90 (2017/10/06)
In the last decade, manganese(II) complexes with N-donor tetradentate aminopyridine ligands emerged as efficient catalysts of enantioselective epoxidation of olefins and direct selective oxidation of C?H groups in complex organic molecules, with environmentally benign oxidant hydrogen peroxide. In this personal account, we summarize the progress of these catalysts with regard to ligands design, structure-reactivity correlations, evaluation of the substrate scope, as well as mechanistic studies, shedding light on the nature of active sites and the mechanisms of selective oxygenations. Several practically promising catalytic syntheses with the aid of Mn aminopyridine catalysts are exemplified.
Highly efficient asymmetric epoxidation of olefins with a chiral manganese-porphyrin covalently bound to mesoporous SBA-15: Support effect
Farokhi, Afsaneh,Hosseini Monfared, Hassan
, p. 229 - 238 (2017/06/19)
A chiral MnIII-porphyrin complex covalently bonded with mesoporous SBA-15 (SBA15-[Mn(TCPP-R?)Cl]) was synthesized and fully characterized. The heterogeneous SBA15-[Mn(TCPP-R?)Cl] exhibited remarkable catalytic activity toward enantioselective olefin epoxidation using O2 as terminal oxidant in the presence of isobutyraldehyde. The catalyst showed higher enantioselectivity than its homogeneous counterpart in the oxidation of α-methylstyrene. SBA15-[Mn(TCPP-R?)Cl] catalyzed epoxidation of styrene was achieved within 8?h and optically active styrene oxide was obtained in 89% ee and 90% yield. Likewise, styrene derivatives (trans-β-methylstyrene, indene), conjugated cis- and trans-disubstituted olefins (e.g. cis- and tans-stilbene) and terminal olefins were converted effectively to their corresponding epoxides in 63–99%?ee under the Mn(III)-catalyzed conditions. The catalyst could be recycled five times without any significant loss in activity.
