- Chemoenzymatic Oxosulfonylation-Bioreduction Sequence for the Stereoselective Synthesis of β-Hydroxy Sulfones
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A series of optically active β-hydroxy sulfones has been obtained through an oxosulfonylation-stereoselective reduction sequence in aqueous medium. Firstly, β-keto sulfones were synthesized from arylacetylenes and sodium sulfinates to subsequently develop the carbonyl reduction in a highly selective fashion using alcohol dehydrogenases as biocatalysts. Optimization of the chemical oxosulfonylation reaction was investigated, finding inexpensive iron(III) chloride hexahydrate (FeCl3 ? 6H2O) as the catalyst of choice. The selection of isopropanol in the alcohol-water media resulted in high compatibility with the enzymatic process for enzyme cofactor recycling purposes, providing a straightforward access to both (R)- and (S)-β-hydroxy sulfones. The practical usefulness of this transformation was illustrated by describing the synthesis of a chiral intermediate of Apremilast. Interestingly, the development of a chemoenzymatic cascade approach avoided the isolation of β-keto sulfone intermediates, which allowed the preparation of chiral β-hydroxy sulfones in high conversion values (83–94 %) and excellent optical purities (94 to >99 % ee).
- González-Sabín, Javier,Gotor-Fernández, Vicente,López-Agudo, Marina,Lavandera, Iván,Ríos-Lombardía, Nicolás
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- Double Asymmetric Hydrogenation of α-Iminoketones: Facile Synthesis of Enantiopure Vicinal Amino Alcohols
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This study presents an Rh/DuanPhos-catalyzed double asymmetric hydrogenation of α-iminoketones for accessing chiral vicinal amino alcohols, which are privileged motifs in pharmaceuticals, agrochemicals, fine chemicals, chiral auxiliaries, organocatalysts, etc. Compared with existing methods, this methodology has the following advantages, such as one-pot operation, high efficiency, operational simplicity, limited waste, broad reaction scope, and high yields (90 to 96%) and stereoselectivities (up to >99:1 dr; >99.9% ee). In addition, the mechanism of the transformation was revealed to be a stepwise reaction by isolating and analyzing reaction intermediates.
- Lin, Xin,Shao, Pan-Lin,Song, Jingyuan,Wang, Jiang,Wen, Jialin,Zhang, Xumu
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p. 12729 - 12735
(2021/10/29)
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- Efficient synthesis of chiral β-hydroxy sulfones: Via iridium-catalyzed hydrogenation
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A highly efficient Ir/f-Amphol-catalyzed asymmetric hydrogenation of prochiral β-keto sulfones was successfully developed to prepare a series of chiral β-hydroxy sulfones with good to excellent results (62%->99% conversions, 35%-99% yields and 86%->99% ee). Our Ir/f-Amphol L4 catalytic system exhibited very high activity; the gram-scale asymmetric hydrogenation was performed well with just 0.005 mol% catalyst loading (S/C = 20,000) to afford the desired product 2a with >99% conversion, 99% yield and 93% ee.
- Tao, Lin,Yin, Congcong,Dong, Xiu-Qin,Zhang, Xumu
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p. 785 - 788
(2019/01/30)
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- Synthesis of γ-sulfonyl δ-lactones and β-sulfonyl styrenes
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A facile route to the synthesis of γ-sulfonyl lactones 5 and β-sulfonyl styrenes 6 has been developed, achieving moderate to good yields via the (1) NaH mediated Michael addition of β-ketosulfones 3 and methyl acrylate in refluxing THF and (2) NaBH4mediated stereoselective reduction/lactonization of δ-ketoesters 4 in boiling MeOH, or (3) boron trifluoride etherate mediated ring-opening of lactones 5 in MeOH at reflux.
- Chan, Chieh-Kai,Chen, Yu-Hsin,Hsu, Ru-Ting,Chang, Meng-Yang
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- Palladium-mediated synthesis of 1,1,2-triarylethanes. Application to the synthesis of CDP-840
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A three-step protocol toward 1,1,2-triarylethanes 1 starting with β-ketosulfones 2 is developed. A facile process is carried out for the (1) reduction of 2 with NaBH4, (2) BF3·OEt2-mediated Friedel-Crafts reactions of the
- Lin, Yi-Shan,Kuo, Yi-Chun,Kuei, Chun-Hsiung,Chang, Meng-Yang
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p. 1275 - 1282
(2017/02/10)
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- Iron-Catalyzed Synthesis of Sulfur-Containing Heterocycles
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An iron-catalyzed synthesis of sulfur- and sulfone-containing heterocycles is reported. The method is based on the cyclization of readily available substrates and proceeded with high efficiency and diastereoselectivity. A variety of sulfur-containing heterocycles bearing moieties suitable for subsequent functionalization are prepared. Illustrative examples of such postcyclization modifications are also presented.
- Bosset, Cyril,Lefebvre, Gauthier,Angibaud, Patrick,Stansfield, Ian,Meerpoel, Lieven,Berthelot, Didier,Guérinot, Amandine,Cossy, Janine
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p. 4020 - 4036
(2017/04/27)
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- Ammonium iodide-induced sulfonylation of alkenes with DMSO and water toward the synthesis of vinyl methyl sulfones
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A novel ammonium iodide-induced sulfonylation of alkenes with DMSO and water toward the synthesis of vinyl methyl sulfones is described. The process proceeded smoothly under metal-free conditions with high stereoselectivity and good functional group toler
- Gao, Xiaofang,Pan, Xiaojun,Gao, Jian,Huang, Huawen,Yuan, Gaoqing,Li, Yingwei
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supporting information
p. 210 - 212
(2015/01/09)
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- Highly enantioselective one-pot synthesis of chiral β-hydroxy sulfones via asymmetric transfer hydrogenation in an aqueous medium
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A mild transformation in an aqueous medium for the one-pot synthesis of optically active β-hydroxy sulfones is described. The intermediates of β-keto sulfones obtained via a nucleophilic substitution reaction of α-bromoketones and sodium sulfinates in Hs
- Zhang, Dacheng,Cheng, Tanyu,Zhao, Qiankun,Xu, Jianyou,Liu, Guohua
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supporting information
p. 5764 - 5767
(2015/02/19)
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- Acid-promoted reaction of sulfonyl chlorides with alkenes: New approach to the regioselective synthesis of β-hydroxyl sulfone derivatives
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Reaction of sulfonyl chlorides with alkenes and water in the presence of catalytic amount of sulfonic acid provided β-hydroxyl sulfone derivatives in high yields.
- Xi, Chanjuan,Lai, Chunbo,Chen, Chao,Wang, Ruji
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p. 1595 - 1597
(2007/10/03)
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- Asymmetric Radical Reaction in the Coordination Sphere. 2. Asymmetric Addition of Alkane- and Arenesulfonyl Chlorides to Olefins Catalyzed by a Ruthenium(II)-Phosphine Complex with Chiral Ligands
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The addition of arenesulfonyl chlorides to styrene in the presence of a catalytic amount of a ruthenium(II) complex with chiral phosphine ligands, Ru2Cl43 or Ru2Cl43, proceeds under mild conditions to give optically active 1:1 adducts,
- Kameyama, Masayuki,Kamigata, Nobumasa,Kobayashi, Michio
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p. 3312 - 3316
(2007/10/02)
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- ACTIVATION DE LA LIAISON C-H FAIBLEMENT ACIDE PAR ADSORPTION SUR KF-Al2O3
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Condesation of poorly acidic carbon compounds (pka 18-30) with benzaldehyde was achieved by adsorption without solvent on KF-Al2O3.KF-Al2O3 appears as a stronger base than KF.
- Villemin, Didier,Ricard, Michele
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p. 1059 - 1060
(2007/10/02)
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- NUCLEOPHILIC ADDITION TO STYRYL SULPHONES. PART I. A STUDY ON THE REGIOCHEMISTRY.
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Styryl sulphones undergo nucleophilic addition, with the nucleophile adding at the α- or the β-position, with respect to the sulphone group; β-attack is normally favoured over α-attack.Factors which can change the regioselectivity in favour of the addition of the nucleophile to the α-position are discussed for heteronucleophiles as well as carbon nucleophiles.
- Benedetti, F.,Fabrissin, S.,Risaliti, A.
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p. 3887 - 3894
(2007/10/02)
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