- Silent catalytic promiscuity in the high-fidelity terpene cyclase δ-cadinene synthase
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δ-Cadinene synthase (DCS) is a high-fidelity sesquiterpene synthase that generates δ-cadinene as the sole detectable organic product from its natural substrate (E,E)-FDP. Previous work with this enzyme using substrate analogues revealed the ability of DCS
- Loizzi, Marianna,Miller, David J.,Allemann, Rudolf K.
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p. 1206 - 1214
(2019/02/07)
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- Synthesis and evaluation of locostatin-based chemical probes towards PEBP-proteins
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Phosphatidyl ethanolamine-binding proteins (PEBPs) are implicated in various critical physiological processes in all eukaryotes. Among them is Flowering Locus T (FT), the protein recently discovered as the vital flowering hormone in plants. Small molecule
- Hoogenboom, Jorin,Fiers, Martijn,Immink, Richard,Zuilhof, Han,Wennekes, Tom
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supporting information
p. 2406 - 2409
(2016/05/19)
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- Asymmetric synthesis of isoquinuclidines by Diels-Alder reaction of 1,2-dihydropyridine utilizing a chiral Lewis acid catalyst
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The chiral isoquinuclidine derivative, 2-azabicyclo[2.2.2]octane ring system, endo-(7R)-3 was obtained in good yield with excellent diastereoselectivity (up to 92% de) by Diels-Alder reaction of 1-(phenoxycarbonyl)-1,2-dihydropyridine 1 with N-acryloyl-(4S)-4- benzyloxazolidin-2-one (4S)-2 using titanium-(2R,3R)-TADDOLate 4 as a chiral Lewis acid catalyst in toluene at 0 °C. On the other hand, endo-(7S)-3 was obtained in good yield with excellent diastereoselectivity (up to 97% de) by Diels-Alder reaction of 1 with (4R)-2 using Cu(OTf)2/(4S,4′S)- bis(oxazoline) catalyst 8 as a chiral Lewis acid catalyst in dichloromethane at 0 °C. In these reactions, the choice of solvent and the combination of titanium-(2R,3R)-TADDOLate 4 {or Cu(II)/(4S,4′S)-bis(oxazoline) 8} and dienophile (4S)-2 {or (4R)-2} are very important. The stereochemistry of endo-(7R)-3 has been established to be (1R,4S,7R) and the reaction mechanism is proposed.
- Seki, Chigusa,Hirama, Masafumi,Hutabarat, N.D.M. Romauli,Takada, Junko,Suttibut, Chonticha,Takahashi, Hideto,Takaguchi, Takuya,Kohari, Yoshihito,Nakano, Hiroto,Uwai, Koji,Takano, Nobuhiro,Yasui, Mitsukuni,Okuyama, Yuko,Takeshita, Mitsuhiro,Matsuyama, Haruo
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experimental part
p. 1774 - 1781
(2012/03/10)
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- Conjugate hydrotrifluoromethylation of α,β-unsaturated acyl-oxazolidinones: Synthesis of chiral fluorinated amino acids
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A novel conjugate hydrofluoroalkylation of α,β-unsaturated acyl-oxazolidinones is described. Using this method, enantiomerically pure β-trifluoromethylated amino acids were prepared. Trifluorovaline and trifluoroisoleucine were incorporated into peptides and found to show extremely low α-helix propensities.
- Erdbrink, Holger,Peuser, Ilona,Gerling, Ulla I. M.,Lentz, Dieter,Koksch, Beate,Czekelius, Constantin
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supporting information
p. 8583 - 8586
(2013/01/15)
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- Diastereoselective aziridination of chiral electron-deficient olefins with N-chloro-N-sodiocarbamates catalyzed by chiral quaternary ammonium salts
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Chiral quaternary ammonium salt-catalyzed diastereoselective aziridination of electron-deficient olefins that possess a chiral auxiliary with N-chloro-N-sodiocarbamates was developed. The key to high stereoselectivity was found to be the employment of the
- Murakami, Yuta,Takeda, Youhei,Minakata, Satoshi
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experimental part
p. 6277 - 6285
(2011/10/02)
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- Enantioselective synthesis of α-methylene-β-hydroxy carboxylic acid derivatives via a diastereoselective aldol/β-elimination sequence: Application to the C(15)-C(21) fragment of tedanolide C
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An enantioselective synthesis of α-methylene-β-hydroxy carboxylic acid derivatives via a highly diastereoselective, one-pot syn-aldol and β-elimination sequence utilizing the chiral β-(phenylselenyl) propionyl imide 15 is described. This new method, which constitutes an alternative to the Baylis-Hillman reaction, has been applied to the synthesis of the C(15)-C(21) fragment of tedanolide C.
- Barth, Roland,Roush, William R.
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supporting information; experimental part
p. 2342 - 2345
(2010/07/13)
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- Towards functionalized silicon-containing α-amino acids: Asymmetric syntheses of sila analogs of homoserine and homomethionine
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The homoserine and homomethionine sila analogs, (R)-HOSi(Me 2)CH2CH(NH2)CO2H ((R)-21) and (R)-MeSCH2Si(Me2)CH2CH(NH2)CO 2H ((R)-24), respectively, were each synthesized in nine steps and in 30 and 23% overall yield, respectively, from commercially available ClSiMe 2CH2Cl. The key step of both syntheses was the asymmetric α-bromination of an Evans amide to introduce the stereogenic center of the amino acids with defined absolute configuration. While the preparation of the homomethionine analog (R)-24 followed the expected pathway, the sila analog of homoserine, (R)-21, was unexpectedly formed during the catalytic hydrogenation of an N3CH2-substituted silane derivative.
- Smith, Richard J.,Bienz, Stefan
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p. 1681 - 1696
(2007/10/03)
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- 2-OXAZOLIDINONES AND THEIR USE AS INHIBITORS OF ANIMAL CELL MOTILITY AND GROWTH
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Cell motility and growth inhibitors, including compounds of the general structural formula (I), and use of the cell motility and cell growth inhibitors, and pharmaceutically acceptable salts, pro-drugs, and solvates thereof, as therapeutic agents, are disclosed.
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- Total synthesis of a conformationally constrained didemnin B analog
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The total synthesis of a didemnin B analogue containing a conformationally constrained replacement for the isostatine moiety is reported. Synthetic highlights include an improved preparation of 2-hydroxy-3-cyclohexenecarboxylic acid and a new strategy for accessing the macrocycle.
- Xiao,Vera,Liang,Joullie
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p. 2734 - 2742
(2007/10/03)
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- Mixed-Ligand Arenechromium Carbonyl Complexes as Electronic Modulators
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A number of mixed ligand η6 arenechromium carbonyl complexes have been prepared and investigated for their ability to effect electronic modulation of arene chemistry. In the case of an aniline-derived system, the arenechromium carbonyl complex is able to modulate the inductive capacity of the aniline nitrogen atom and thus, regulate its anchimeric ability. In the case of 8-phenylmenthol and benzyloxazolidinone derivatives, modulation of arene π basicity is achieved, and results suggest that important vinylarene π-π interactions exist in acrylate derivatives of these chiral auxiliary systems.
- Jones, Graham B.,Chapman, Brant J.,Mathews, Jude E.
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p. 2928 - 2938
(2007/10/03)
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- Synthesis of β,γ-unsaturated N-acyl-2-oxazolidinones
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An effective imide formation method is presented, which allows the preparation of β,γ-unsaturated N-acyl-2-oxazolidinones with high yields and without isomerization of the double bond to give the α,β-unsaturated isomers, which are the inevitable by-products when alternative procedures are used.
- Dobarro, Alicia,Velasco, Dolores
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p. 13733 - 13738
(2007/10/03)
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- Synthesis of β,γ-unsaturated N-acyl-2-oxazolidinones
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An effective imide formation method is presented, which allows the preparation of β,γ-unsaturated N-acyl-2-oxazolidinones with high yields and without isomerization of the double bond to give the α,γ-unsaturated isomers, which are the inevitable by-products when alternative procedures are used.
- Dobarro, Alicia,Velasco, Dolores
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p. 13525 - 13530
(2007/10/03)
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- Process of synthesizing n-acyl auxiliaries
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A process of synthesizing N-acyl auxiliary compounds is disclosed. A compound of the formula: STR1 is reacted with an anhydride in the presence of a lithium salt and an amine base to produce the N-acylated auxiliary.
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- A practical method for N-acylation of bornane-2,10-sultam and 2-oxazolidinones
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The N-trimethylsilyl derivatives of (+)-bornane-2,10-sultam (10,10-dimethyl-5-thia-4-azatricyclo[5.2.1.03,7]decane 5,5-dioxide) and (R)-4-benzyl-2-oxazolidinone and 4-methyl-5-phenyl-2-oxazolidinone react with acid chlorides in refluxing benzen
- Thom,Kocienski
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p. 582 - 586
(2007/10/02)
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