- Stereoselective synthesis of chiral δ-lactonesviaan engineered carbonyl reductase
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A carbonyl reductase variant,SmCRM5, fromSerratia marcescenswas obtained through structure-guided directed evolution. The variant showed improved specific activity (U mg?1) towards most of the 16 tested substrates and gave high stereoselectivities of up to 99% in the asymmetric synthesis of 13 γ-/δ-lactones. In particular, SmCRM5showed a 13.8-fold higher specific activity towards the model substrate,i.e., 5-oxodecanoic acid, and gave (R)-δ-decalactone in 99% ee with a space-time yield (STY) of 301 g L?1d?1. The preparative synthesis of six δ-lactones in high yields and with high enantiopurities showed the feasibility of the biocatalytic synthesis of these high-value-added chemicals, providing a cost-effective and green alternative to noble-metal catalysis.
- Wang, Tao,Zhang, Xiao-Yan,Zheng, Yu-Cong,Bai, Yun-Peng
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p. 10584 - 10587
(2021/10/19)
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- Efficient Stereoselective Synthesis of Structurally Diverse γ- and δ-Lactones Using an Engineered Carbonyl Reductase
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Structurally diverse γ- and δ-lactones were efficiently synthesized stereoselectively using an engineered carbonyl reductase from Serratia marcescens (SmCRV4). SmCRV4 exhibited improved activity (up to 500-fold) and thermostability toward 14 γ-/δ-keto acids and esters, compared with the wild-type enzyme, with 110-fold enhancement in catalytic efficiency (kcat/Km) toward methyl 4-oxodecanoate. The preparative synthesis of alkyl and aromatic γ- and δ-lactones with 95 %–>99 % ee and 78 %–90 % yields was demonstrated. The highest space-time yield, 1175 g L?1 d?1, was achieved for (R)-γ-decalactone.
- Chen, Meng,Zhang, Xiao-Yan,Xing, Chen-Guang,Zhang, Chao,Zheng, Yu-Cong,Pan, Jiang,Xu, Jian-He,Bai, Yun-Peng
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p. 2600 - 2606
(2019/05/21)
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- Preparation method of (R)-(+)-gamma-amylbutyrolactone and (R)-(-)-gamma-amylbutyrolactone
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The invention discloses a preparation method of (R)-(+)-gamma-amylbutyrolactone and (R)-(-)-gamma-amylbutyrolactone. The preparation method comprises (1) carrying out ring opening on racemic gamma-amylbutyrolactone by an inorganic alkali solution to obtain an aqueous solution of gamma-hydroxy acid-base metal salt, then adding an organic solvent into the solution, adjusting the mixed solution to weak acidity through an inorganic acid so that the produced gamma-hydroxy acid enters an organic phase, separating the organic phase and carrying out drying, (2) adding (S)-(-)-alpha-phenethylamine or (R)-(+)-alpha-phenethylamine into the obtained organic phase, carrying out crystallization to obtain low optical activity gamma-hydroxy acid phenylethylamine salt, and (3) adding the obtained amine salt into a resolving solvent, carrying out stirring for dissolution, carrying out crystallization and filtration, dissolving the filter cake through water, adding an inorganic acid into the solution, carrying out acidification cyclization, and extracting R)-(+)-gamma-amylbutyrolactone or (S)-(-)-alpha-phenethylamine through an organic solvent. The splitting method is easy to operate and can acquiretwo configurations of chiral gamma-phenethylamine. The products have pure and natural aroma. The preparation method has the advantages of simple processes, mild conditions and high enantiomeric excess.
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- Simple Preparation of Rhodococcus erythropolis DSM 44534 as Biocatalyst to Oxidize Diols into the Optically Active Lactones
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In the current study, we present a green toolbox to produce ecological compounds like lactone moiety. Rhodococcus erythropolis DSM 44534 cells have been used to oxidize both decane-1,4-diol (2a) and decane-1,5-diol (3a) into the corresponding γ- (2b) and δ-decalactones (3b) with yield of 80% and enantiomeric excess (ee)?=?75% and ee?=?90%, respectively. Among oxidation of meso diols, (?)-(1S,5R)-cis-3-oxabicyclo[4.3.0]non-7-en-2-one (5a) with 56% yield and ee?=?76% as well as (?)-(2R,3S)-cis-endo-3-oxabicyclo[2.2.1]dec-7-en-2-one (6a) with 100% yield and ee?=?90% were formed. It is worth mentioning that R. erythropolis DSM 44534 grew in a mineral medium containing ethanol as the sole source of energy and carbon Chirality 28:623–627, 2016.
- Martinez-Rojas, Enriqueta,Olejniczak, Teresa,Neumann, Konrad,Garbe, Leif-Alexander,Boraty?ski, Filip
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p. 623 - 627
(2016/10/11)
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- Concise total synthesis of (-)-auxofuran by a click Diels-Alder strategy
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The first synthesis of auxofuran, a newly discovered auxin-like signaling molecule of streptomycetes, has been achieved in seven steps and 59% overall yield from commercial starting materials. Central to the synthetic route is a click-unclick Diels-Alder
- Boukouvalas, John,Loach, Richard P.
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p. 4912 - 4914
(2013/10/08)
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- Cyclodextrin-based ionic liquids as enantioselective stationary phases in gas chromatography
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New permethylated mono-6-deoxy-6-pyridin-1-ium and mono-6-deoxy-6-(1-vinyl- 1H-imidazol-3-ium)-α- and -β-cyclodextrin trifluoromethanesulfonate ionic liquids were synthesized from the corresponding permethylated mono-6-hydroxycyclodextrins in a one-pot reaction and solvent-free procedure. Regioselective transformation of native α- and β-cyclodextrins with the use of a bulky tert-butyldiphenylsilyl protecting group afforded the desired 6-monosubstituted permethylated cyclodextrin derivatives in moderate yields. The new ionic liquids were tested as stationary phases in capillary GC columns towards chiral discrimination in enantio-GC analysis of racemic mixtures. The permethylated 6-deoxy-6-pyridin-1-ium-α-cyclodextrin trifluoromethanesulfonate displayed good enantiomeric separations for some racemic esters and lactones, as well as epoxides. In particular, for both the racemic whiskey lactone and the high boiling point menthyl laurate, not successfully separated in a commercial cyclodextrin phase, the enantiomeric separations were achieved isothermally at 140 °C. In phase: Permethylated mono-6-hydroxy-α- and -β-cyclodextrins react with pyridine or 1-vinylimidazole in the presence of triflic anhydride in a solvent-free procedure to yield new roomerature ionic liquids (ILs). These ILs have been used as stationary phases in gas chromatography; enantiomeric separations are achieved (see figure for whiskey lactone) with permethylated mono-6-deoxy-6-(pyridin-1-ium)-α-cyclodextrin trifluoromethanesulfonate. Copyright
- Costa, Nuno,Matos, Sara,Da Silva, Marco D. R. Gomes,Pereira, M. Manuela A.
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p. 1466 - 1474
(2014/01/06)
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- Biocatalytic oxidation of 1,4-diols and γ-lactols into γ-lactones: Application to chemoenzymatic synthesis of drospirenone
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Oxidation of 1-alkyl-1,4-butanediols with Acetobacter aceti MIM 2000/28 gave the corresponding γ-lactones in good yields. The biotransformation occurred with intermediate formation of γ-lactols, which are also substrates for oxidation with Acetobacter aceti MIM 2000/28, as validated by selective biotransformation of 6β,7β;15β,16β-dimethylene-3- oxo-17α-pregn-4-en-21,17-carbolactol to drospirenone.
- Romano, Diego,Contente, Martina,Granato, Tiziana,Remelli, William,Zambelli, Paolo,Molinari, Francesco
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p. 735 - 737
(2013/07/26)
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- Regiodivergent epoxide opening (REO) via electron transfer: Control elements
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The first regiodivergent opening of unbiased epoxides (REO) providing the ring-opened products in high enantiomeric excess from racemic and exceptionally high enantiomeric excess from enantioenriched substrates in a double asymmetric process has been devised. It constitutes a more general case of the very important enantioselective openings of meso-epoxides. The dependence of the selectivity of ring opening on the epoxides substitution pattern was studied.
- Gansaeuer, Andreas,Shi, Lei,Keller, Florian,Karbaum, Peter,Fan, Chun-An
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experimental part
p. 1361 - 1369
(2010/11/03)
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- Synthesis of optically active γ-valerolactone and γ-nonanolactone via optical resolution using chiral amine derived from amino acid
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Optically active γ-valerolactone and γ-nonanolactone have been synthesized via optical resolution using a newly developed chiral amine derived from L-phenylalanine. Both racemic γ-lactones were transformed to corresponding diastereomeric amides by amidation with the optical resolution agent. Fractional crystallization of diastereomeric amides, recrystallization of each diastereomer, and subsequent hydrolysis gave optically active γ-valerolactone and γ-nonanolactone with sufficient enantiomeric excess and isolated yield. The optical resolution agent was recovered after hydrolysis.
- Yumoto, Kenichi,Hasegawa, Morifumi,Toshima, Hiroaki
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experimental part
p. 421 - 431
(2010/09/05)
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- Combination of novozym 435-catalyzed hydrolysis and mitsunobu reaction for production of (r)γ-lactones
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Chiral-lactones of both enantiomers were synthesized with more than 90% optical purities. The key step was Novozym 435-catalyzed hydrolysis of racemic N-benzyl-4-acetoxyalkylamides. Additionally, because (R)-γ-lactones are predominant in apricot, mango, peach, passion fruit, and strawberry, synthesis was attempted using only one enantiomer selectively. The (R)-enantimer was synthesized with more than 80% total yield and more than 90% optical purity by a combination of Novozym 435-catalyzed hydrolysis and the Mitsunobu reaction. Copyright
- Shimotori, Yasutaka,Miyakoshi, Tetsuo
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experimental part
p. 1607 - 1613
(2010/06/21)
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- A mild biosynthesis of lactones via enantioselective hydrolysis of hydroxynitriles
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We have developed a biocatalytic method to produce lactones and related compounds via the enzymatic hydrolysis of γ- and β-hydroxynitriles. The synthesis is a mild, general, and environmentally friendly way to enantioselectively hydrolyze nitriles with commercially available nitrilase enzymes. The synthesis of four pheromones is demonstrated via a one-step method.
- Pollock, Julie A.,Clark, Karen M.,Martynowicz, Bethany J.,Pridgeon, Matthew G.,Rycenga, Matthew J.,Stolle, Kristen E.,Taylor, Stephen K.
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p. 1888 - 1892
(2008/02/12)
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- Development of a solid-phase 'asymmetric resin-capture-release' process: Application of an ephedrine chiral resin in an approach to γ- butyrolactonest
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The potential of a solid-phase asymmetric resin-capture-release strategy for high-throughput synthesis has been evaluated. Fukuzawa's Sm(II)-mediated, asymmetric approach to γ-butyrolactones was selected to illustrate the feasibility of such a process. α,β-Unsaturated esters immobilised on an ephedrine chiral resin have been applied in an asymmetric approach to γ-butyrolactones. Lactone products are obtained in moderate isolated yields with selectivities up to 96% ee. In addition, we have shown that the ephedrine resin can be conveniently recovered and recycled although in some cases lower yields were obtained on reuse of the chiral resin. A short synthesis of a moderate DNA-binding microbial metabolite using asymmetric resin-capture-release is also described.
- Kerrigan, Nessan J.,Hutchison, Panee C.,Heightman, Tom D.,Procter, David J.
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p. 2476 - 2482
(2007/10/03)
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- Stereochemical aspects of the Beckman rearrangement of oximes of levoglucosenone and its dihydro derivative. Enantioselective synthesis of (+)-γ-pelargonolactone
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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.
- Valeev,Gorobets,Tsypysheva,Singizova,Kalimullina,Safarov,Shitikova,Miftakhov
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p. 563 - 568
(2007/10/03)
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- Application of an ephedrine chiral linker in a solid-phase, 'asymmetric catch-release' approach to γ-butyrolactones
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A Sm(II)-mediated, asymmetric, intermolecular ketyl-olefin addition employing α,β-unsaturated esters linked to resin through an ephedrine 'chiral link' has been applied in a direct 'asymmetric catch-release' approach to γ-butyrolactones.
- Kerrigan, Nessan J.,Hutchison, Panee C.,Heightman, Tom D.,Procter, David J.
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p. 1402 - 1403
(2007/10/03)
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- Convenient enantioselective synthesis of new 1,4-sulfanylalcohols from γ-lactones
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A synthetic strategy based upon three basic reactions - enzymatic resolution, oxygen-sulfur exchange, reduction - allowed us to carry out an easy and useful synthesis of a series of new 1,4-sulfanylalcohols from aliphatic γ-lactones. Final products have been obtained in good yields with enantiomeric excesses in a 66-91% range.
- Filippi, Jean-Jacques,Fernandez, Xavier,Lizzani-Cuvelier, Louisette,Loiseau, André-Michel
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p. 6267 - 6270
(2007/10/03)
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- Microbial bioreductions of γ- and δ-ketoacids and their esters
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A series of yeasts were used in the bioreductions of aliphatic and aromatic γ- and δ-ketoacids and esters to investigate the preparation of enantiomerically pure γ- and δ-lactones through the intermediacy of their corresponding γ- and δ-hydroxyacids and esters. Bioreduction of ethyl 4-oxononanoate 2a with Pichia etchellsii afforded the γ-nonanolide (+)-5a with 99% e.e., while Pichia minuta proved to be the best choice for the bioreduction of ethyl 2-oxocyclohexylacetate 2e, which afforded cis-(-)-5e and trans-(-)-5e with 98 and 99% e.e., respectively. Reduction of 3-(2-oxocyclohexyl)propionic acid 3e with Pichia glucozyma gave predominantly the corresponding δ-lactone trans-(-)-6e with 94% e.e., whose absolute configuration was determined by means of CD spectroscopy.
- Forzato, Cristina,Gandolfi, Raffaella,Molinari, Francesco,Nitti, Patrizia,Pitacco, Giuliana,Valentin, Ennio
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p. 1039 - 1046
(2007/10/03)
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- Facile synthesis of optically active γ-lactones via lipase-catalyzed reaction of 4-substituted 4-hydroxybutyramides
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Lipase-catalyzed transesterification of racemic 4-substituted 4- hydroxybutyramides with succinic anhydride proceeded enantioselectively to afford (S)-succinic acid monoester and unreacted (R)-4-hydroxybutyramide derivative, which were separated easily by
- Matsumura, Yasufumi,Endo, Teruko,Chiba, Mitsuo,Fukawa, Hidemichi,Terao, Yoshiyasu
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p. 304 - 305
(2007/10/03)
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- Optical resolution of fragrant lactones
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Optical resolution of six chiral fragrant lactones (δ-jasmine lactone, massoia lactone, tuberolactone, pentynyllactone, δ-decalactone, and γ- nonalactone) was investigated by means of either the diastereomeric salt formation method or the diastereomeric amide formation method. Using these procedures, we obtained each enantiomer from five of the six lactones, except for massoia lactone. All five lactones were obtained in a good yield and with high optical purity. Sensoric characteristics on both enantiomers and racemic modification of four lactones are given.
- Nohira, Hiroyuki,Mizuguchi, Keiko,Murata, Toru,Yazaki, Yuko,Kanazawa, Miho,Aoki, Yoshio,Nohira, Misako
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p. 1359 - 1370
(2007/10/03)
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- Comparison of Routes for the Preparation of Optically Active 7-Ethylbicyclohept-2-en-6-one and -6-ols by Classical Resolution and by an Enzyme-catalysed Biotransformation: Synthesis of γ-Nonalactone
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The optically active ketone 4 has been converted into γ-nonalactone , utilising a photo-induced rearrangement in the key step.Reduction of the ketone (+/-)-3 with Mortierella isabellina gave the alcohols (1S,5S,6R,7S)-7 and (1R,5R,6R,7R)-8 of low optical purity.
- Coughlin, Phillip E.,Godtfredsen, Sven E.,Roberts, Stanley M.,Willetts, Andrew J.
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p. 2789 - 2798
(2007/10/02)
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- Stereochemistry of the Microbial Generation of δ-Decanolide, γ-Dodecanolide, and γ-Nonanolide from C18 13-Hydroxy, C18 10-Hydroxy, and C19 14-Hydroxy Unsaturated Fatty Acids
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(S)-δ-Decanolide (4) was isolated from cultures of Cladosporium suaveolens after the microorganism was fed either (S)- or (R,S)-coriolic acid (1).Feeding (R,S)-10-hydroxyoctadec-(8E)-enoic acid (2) to Yarrowia lipolytica produced (S)-γ-dodecanolide.When (S)-homocoriolic acid (3) was fed to C. suaveolens, γ-nonalide slightly enriched in the S enantiomer was produced.At some stage in the biodegradation of 3, an inversion of configuration, from S to R, occured and was accompanied by the loss of the hydrogen atom originally present on C-14, as GLC/MS analysis of the products of feeding C. suaveolens with deuterated 10 showed.
- Cardillo, Rosanna,Fronza, Giovanni,Fuganti, Claudio,Grasselli, Piero,Mele, Andrea,et al.
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p. 5237 - 5239
(2007/10/02)
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- Bakers' yeast reduction of γ and δ ketonitriles: Intermediates for the synthesis of (S)-5-hexanolide and other chiral lactones
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A number of γ and δ ketonitriles have been synthesized and their reduction with bakers' yeast carefully studied. Both 4-oxopentanenitrile and 5-oxohexanenitrile are reduced in moderate yields to the corresponding (S) alcohols of high ee while other substrates gave products of varying optical purities. These alcohols are useful intermediates for the preparation of chiral lactones, including the synthetically important (S)(-)-4-methylbutyrolactone and (S)-5-hexanolide.
- Gopalan,Lucero,Jacobs,Berryman
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p. 1321 - 1329
(2007/10/02)
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- 1,4-Addition of Optically Active Transferable Ligands from Organocuprates. Generation and Reaction of Homochiral α-Alkoxyorganocuprates
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Homochiral higher order cyano α-alkoxyorganocuprate addition to ynoates and enones occurs with 0-97percent retention of configuration; results that imply multiple reaction pathways may be operative in 1,4-addition of these species.
- Linderman, Russell J.,Griedel, Brian D.
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p. 5428 - 5430
(2007/10/02)
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- ENZYMATIC RESOLUTION OF RACEMIC LACTONES
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PPL, HLE or PLE enzymatic resolution of racemic γ, δ and ε-lactones gives optically active lactones (ee: 60 to 90percent).
- Blanco, L.,Guibe-Jampel, E.,Rousseau, G.
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p. 1915 - 1918
(2007/10/02)
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- Asymmetric Reduction of a Prochiral Carbonyl Group of Aliphatic γ- and δ-Keto Acids by Use of Fermenting Bakers' Yeast
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With use of fermenting bakers' yeast, γ- and δ-keto acids, RCO(CH2)nCO2H (n = 2 and 3; R = C2H5, n-C3H7, n-C4H9, n-C5H17, n-C8H11, n-C11H23 and n-C13H27), were reduced to the corresponding γ- and δ-hydroxy acids which were isolated as γ- and δ-lactones in low to good yields with >98percent ee.The shortest γ- and δ-keto acid (R = CH3) failed to give the hydroxy acids.The reduction of 5-oxohexadecanoic acid (n = 3; R = n-C11H23) was examined under various conditions to improve the chemical yield.The absolute configurations of all of the lactones were determined to be R, even though the Prelog rule predicts the S configurations for the substrates having R = C2H5 and n-C3H7.The role of the carboxy group was discussed in comparison with the results obtained for the δ-keto esters.
- Utaka, Masanori,Watabu, Hisashi,Takeda, Akira
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p. 4363 - 4368
(2007/10/02)
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- Synthesis of the optical antipodes of 4-alkyl-γ-lactones
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Optical antipodes of 4-alkyl-γ-lactones 3 have been prepared by photochemical rearrangement of optically active α,β-epoxy diazomethyl ketones 1 in ethanol to give 4-hydroxy-alkenoates 2, followed by reduction of the alkene bond and subsequent lactonization.The required epoxy diazomethyl ketones 1 were obtained via the following sequence of reactions: alkylation of 2-propyn-1-ol, subsequent reduction to the alkenols 6, Sharpless epoxidation to 2,3-epoxy alcohols 7, oxidation to glycidic esters 8 and finally conversion to diazo ketones 1.The enantiomeric purities range from 84 to 100percent.
- Thijs, Lambertus,Waanders, Peter P.,Stokkingreef, Edwin H. M.,Zwanenburg, Binne
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p. 332 - 337
(2007/10/02)
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- A Facile and General Entry to Optically Active Pheromones and Aromas With γ-Alkyl-γ-lactone Structures. A Study of Some Lactone Derivatives of Pentoses
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A new and easy general methodology has been developed to prepare γ-alkyl-α,β-butenolides or γ-alkylbutyrolactones in four and five steps, respectively, from D-ribonolactone as a common chiral starting material.Some of these products have pheromonal activity in insects and are also used as fruit fragrances.A study on several derivatives of D-ribonolactone and 2-deoxy-D-ribonolactone has been carried out in order to explore alternative routes for these syntheses.
- Cardellach, J.,Font, J.,Ortuno, R. M.
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p. 327 - 331
(2007/10/02)
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- Synthesis of Both the Enantiomers of (2Z,6Z)-2,6-Nonadien-4-olide, the Possible Male-Secreted Sex Pheromone from a Pyralid Moth, Aphomia gularis Zeller
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Both the enantiomers (ca. 96percent e.e.) of (2Z,6Z)-2,6-nonadien-4-olide, a possible pheromone of Aphomia gularis, were synthesized by resolving an acetylenic intermediate.
- Miyashita, Yasuo,Mori, Kenji
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p. 2521 - 2526
(2007/10/02)
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- PREPARATION D'ALKYL-4 γ-LACTONES OPTIQUEMENT ACTIVES
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Highly pure enantiomers of 4-alkyl γ-lactones are synthesized from optically active propargylic carbinols obtained by asymmetric reduction of α-acetylenic ketones with the chiral complex (LiAlH4, N-methylephedrine-3,5 dimethylphenol).
- Vigneron, J. P.,Bloy, V.
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p. 1735 - 1738
(2007/10/02)
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