- Synthesis of simple enantiopure tetrahydro-β-carbolines and tetrahydroisoquinolines
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Enantioselective hydrogenation of the imines 11-13, 27 and 30 with the Ru complex (R,R)-5 led to the tetrahydro-β-carbolines (1S)-14, (1R)-21 and (1S)-22, and the tetrahydroisoquinoline (1S)-31 with ee > 95%. By employing (S,S)-5 the enantiomers are accessible. The imines 11-12 and 27 were obtained by oxidation of racemic 14, 21 and 22 with KMnO4 in > 58% yield.
- Tietze, Lutz F.,Zhou, Yifa,Toepken, Enno
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- A four-hydrogenated 1, 8 - naphthyridine apperception composition preparation method and its prepared chiral products
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The invention discloses a preparation method of a tetrahydro 1, 8-naphthyridine compound. The preparation method comprises the following steps: under the existence of a chiral catalyst, enabling a compound with the structure shown in the formula (1) (in the description) and hydrogen to be subjected to addition reaction, wherein the chiral catalyst is a coordination compound with the structure shown in the formula (2) (in the description). The invention further provides a chiral product of the tetrahydro 1, 8-naphthyridine compound, prepared through the preparation method. According to the invention, the proper compound with the structure shown in the formula (1) (in the description) is used as a substrate, and the proper coordination compound with the structure shown in the formula (2) (in the description) is used as the chiral catalyst to perform selective hydrogenation reduction on 1, 8-naphthyridine compound with the structure shown in the formula (1) by adopting hydrogen, so that the chiral product of the tetrahydro 1, 8-naphthyridine compound is prepared with low cost. The chiral product of the tetrahydro 1, 8-naphthyridine compound can be used as a biologically active compound and a structural building block of a chiral drug.
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Paragraph 0137
(2018/03/26)
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- O-bicyclic amine compounds as well as preparation method and chiral products thereof
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The invention relates to the field of asymmetric synthesis methods, and discloses a preparation method of o-bicyclic amine compounds. The method comprises the step of enabling a compound having a structure as shown in a formula (1) and hydrogen to be subjected to an addition reaction in presence of a chiral catalyst, wherein the chiral catalyst is a complex having a structure as shown in a formula (2). The invention also provides chiral products of the o-bicyclic amine compounds prepared by the method, and the o-bicyclic amine compounds. After the method is adopted, the selective hydrogenation reduction of the compound having the structure as shown in the formula (1) is realized by using the hydrogen, so that octahydrogenated products, i.e., the o-bicyclic amine compounds shown in a formula (4) are produced with low cost. The formula (1), the formula (2) and the formula (4) are described in the description.
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Paragraph 0078; 0148-0149
(2017/11/04)
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- A four-hydrogenated 1, 5 - naphthyridine apperception composition preparation method and its prepared chiral products
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The invention discloses a method for preparing a tetrahydro-1,5-naphthyridine compound. The method comprises the following steps: carrying out an addition reaction between a compound with the structure shown as a formula (1) and hydrogen in the presence of a chiral catalyst, wherein the chiral catalyst is a coordination complex with a structure shown as a formula (2). The invention also provides a chiral product of the tetrahydro-1,5-naphthyridine compound prepared by the method. The proper compound with the structure shown as the formula (1) is selected as a substrate, the proper coordination complex with the structure shown as the formula (2) is selected as the chiral catalyst, and selective hydrogenation reduction of the 1,5-naphthyridine compound with the structure shown as the formula (1) is realized by adopting hydrogen, so that the chiral product of the tetrahydro-1,5-naphthyridine compound is prepared at low cost. The chiral product of the tetrahydro-1,5-naphthyridine compound prepared by the invention can serve as a structure block of bioactive compounds and chiral drugs.
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Paragraph 0138
(2017/08/25)
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- (1R,2R)-(+)-(1,2)-DPEN-Bonded Sulfonic Acid Resin: A Trifunctional Heterogeneous Catalyst for Asymmetric Michael Additions of Acetone to Nitroolefins
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Based on (1R,2R)-(+)-(1,2)-DPEN skeleton, a series of primary amine-sulfamide bifunctional catalysts were synthesized, which exhibited excellent catalytic performance in the Michael addition of acetone to β-nitrostyrene. Therefore, a trifunctional heterogeneous catalyst was designed and prepared by simple N-sulfonyl reaction of (1R,2R)-(+)-(1,2)-DPEN and sulfonyl chloride resin. It was employed for the aforementioned addition without any additive and satisfactory results (80.5% conversion; 84.3% ee) were obtained. Meanwhile, the structural and textural properties of the catalyst were characterized by infrared spectroscopy (FT-IR), elemental analysis, SEM, and N2 adsorption and desorption experiments. Finally, the generality of the catalyst was investigated.
- Zhang, Chao,Li, Jing,Tian, Jun,Fang, Wangwang,Li, Yang,Chen, Ligong,Yan, Xilong
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supporting information
p. 1248 - 1258
(2015/03/30)
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- COMPOSITIONS AND METHODS FOR CYCLOFRUCTANS AS SEPARATION AGENTS
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The present invention relates to derivatized cyclofructan compounds, compositions comprising derivatized cyclofructan compounds, and methods of using compositions comprising derivatized cyclofructan compounds for chromatographic separations of chemical species, including enantiomers. Said compositions may comprise a solid support and/or polymers comprising derivatized cyclofructan compounds.
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Page/Page column 44
(2010/12/31)
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- Organocatalytic michael addition of 1,3-dicarbonyl indane compounds to nitrostyrenes
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To map out the efficient organocatalyst requirements in the Michael addition of 1,3-dicarbonyl indane compounds to nitrostyrenes, a dozen different amino organocatalysts containing a p-toluenesulfonyl group (Ts) have been evaluated; excellent enantioselectivities (up to er 92:8) were obtained with a primary amine-based Ts-DPEN catalyst and a plausible catalytic reaction mechanism was proposed on the basis of the experimental results. Copyright
- Jiang, Zhen-Yu,Yang, Hua-Meng,Ju, Ya-Dong,Li, Li,Luo, Meng-Xian,Lai, Guo-Qiao,Jiang, Jian-Xiong,Xu, Li-Wen
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scheme or table
p. 2551 - 2563
(2010/07/08)
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- Enantioselective Michael addition of ketones to maleimides catalyzed by bifunctional monosulfonyl DPEN salt
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An unprecedented enantioselective Michael addition of various ketones to maleimides catalyzed by a simple bifunctional primary amine, monosulfonyl DPEN salt, is reported and provides the desired adducts in good to excellent yields (up to 99%) with excellent enantioselectivities (up to 99%).
- Yu, Feng,Sun, Xiaomin,Jin, Zhichao,Wen, Shigang,Liang, Xinmiao,Ye, Jinxing
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supporting information; experimental part
p. 4589 - 4591
(2010/11/18)
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- Asymmetric de novo synthesis of fluorinated d-glucitol and d-mannitol analogues
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A highly efficient anti-SE2′ electrophilic fluorination of enantioenriched allylsilanes a subsequent dihydroxylation of the resulting allylic fluorides were used as key steps for the synthesis of three fluorinated carbohydrate analogues, 1,5-di-O-benzyl-2-deoxy-2-fluoro-d-glucitol, 2,6-di-O-benzyl-5-deoxy-5-fluoro-l-glucitol and 1,5-di-O-benzyl-2-deoxy-2-fluoro-d-mannitol. A new catalytic asymmetric route to 1-benzyloxy-4-trimethylsilyl-but-3-yn-2-ol, a common precursor to two advanced allylsilanes, is also described featuring a Noyori asymmetric transfer hydrogenation reaction.
- Giuffredi, Guy T.,Purser, Sophie,Sawicki, Marcin,Thompson, Amber L.,Gouverneur, Veronique
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experimental part
p. 910 - 920
(2009/09/25)
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- Vanadium-catalyzed asymmetric epoxidation of allylic alcohols in water
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Asymmetric V-catalyzed epoxidation of allylic alcohols can be carried out in water with chiral ligands, which incorporate sulfonamide and hydroxamic acid fragments. Furthermore, the reaction, notorious for its ligand-deceleration effect, in water turned into the ligand-accelerated process. By using this aqueous protocol, a range of allylic alcohols were epoxidized with up to 94% ee.
- Malkov, Andrei V.,Czemerys, Louise,Malyshev, Denis A.
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supporting information; experimental part
p. 3350 - 3355
(2009/09/26)
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- Ru-catalyzed enantioselective preparation of methyl (R)-o-chloromandelate and its application in the synthesis of (S)-Clopidogrel
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The preparation of methyl (R)-o-chloromandelate via Ru-catalyzed asymmetric hydrogenation and transfer hydrogenation was investigated. With Ru-(R,R)-2,4,6-triisopropyl C6H2SO2-DPEN as the catalyst and HCOOH-Et3N azeotrope as the hydrogen donor, up to 92% ee was obtained in an optional condition. The synthesis of (S)-Clopidogrel was also studied.
- Yin, Lu,Shan, Wenjun,Jia, Xian,Li, Xingshu,Chan, Albert S.C.
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experimental part
p. 2092 - 2095
(2009/10/31)
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- Enantioselective total synthesis of (S)-(-)-quinolactacin B
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The enantioselective total synthesis of (-)-quinolactacin B (-)-1 was performed in seven steps and 33% overall yield from tryptamine. The synthesis features the use of ruthenium catalytic asymmetric hydrogen reaction to introduce the chirality in dihydro-
- Shankaraiah, Nagula,da Silva, Wender A.,Andrade, Carlos Kleber Z.,Santos, Leonardo Silva
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p. 4289 - 4291
(2008/09/21)
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- Asymmetric Syn-selective Henry reaction catalyzed by the sulfonyldiamine-CuCl-pyridine system
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(Chemical Equation Presented) A catalytic asymmetric Henry reaction has been developed with use of a sulfonyldiamine-CuCl complex as a catalyst. A series of new binaphthyl-containing sulfonyldiamine ligands (2a-h) were readily synthesized in two steps starting from commercially available chiral 1,2-diamines. The (R,R)-diamine-(R)-binaphthyl ligand (2d)-CuCl complex smoothly catalyzed the enantioselective Henry reaction with the assistance of pyridine to give the corresponding adduct with high enantiomeric excess (up to 93%). Moreover, the 2d-CuCl-pyridine system promotes the diastereoselective Henry reaction in syn-selective manner to give the adduct in up to 99% yield with 92:8 synlanti selectivity. The enantiomeric excess of the syn-adduct was 84% ee.
- Arai, Takayoshi,Takashita, Ryuta,Endo, Yoko,Watanabe, Masahiko,Yanagisawa, Akira
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p. 4903 - 4906
(2008/12/20)
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- The synthesis of chiral N-tosylatedaminoimine ligands and their application in enantioselective addition of phenylacetylene to imines
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A class of new chiral tridentate N-tosylatedaminoimine ligands were synthesized and used in the Cu(I)-catalyzed enantioselective addition of phenylacetylene to imines. Good enantioselectivities in up to 91% ee were obtained.
- Liu, Bao,Liu, Juntao,Jia, Xian,Huang, Ling,Li, Xingshu,Chan, Albert S.C.
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p. 1124 - 1128
(2008/02/08)
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