Synthesis of perfluoroalkylated sugars catalyzed by rabbit muscle aldolase (RAMA)

Zhu, Wei; Li, Zuyi

doi:10.1039/a910336h

Cited by 14 publications

(6 citation statements)

References 17 publications

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“…Both type I and type II enzymes have been isolated from different prokaryotic and eukaryotic sources and thus, FBP aldolase is an ubiquitous glycolytic enzyme that plays a crucial role in glycolysis, gluconeogenesis, and fructose metabolism. The class I FBP aldolase isolated from rabbit muscle (RAMA) is the aldolase most frequently employed in organic synthesis, followed by type II aldolases from yeast and bacteria, due to their commercial availability. − …”

Section: Enzymatic Aldol Reactionsmentioning

confidence: 99%

C−C Bond-Forming Lyases in Organic Synthesis

et al. 2011

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Section: Enzymatic Aldol Reactionsmentioning

confidence: 99%

C−C Bond-Forming Lyases in Organic Synthesis

et al. 2011

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“…[7] To a solution of vinyl ether 1a (0.22 g, 1.0 mmol), CH 3 CN (1.2 mL), water (1.0 mL) and 1-iodoperfluoroalkane (1.3 mmol) at 0°C (for perfluorooctyl iodide a 20°C water bath was used) under N 2 were added NaHCO 3 (0.11 g, 1.3 mmol) and sodium dithionite (Na 2 S 2 O 4 ) (0.23 g, 1.3 mmol). The resulting solution was stirred overnight; H 2 O was then added, and the hydrolysate was extracted with DCM.…”

Section: Investigations Based On 1amentioning

confidence: 97%

“…With dihydropyranyl vinyl ether 11a at hand 1-iodoperfluoroalkane addition was performed. [7] All three iodides used gave the corresponding addition product, 2-ethoxy-4-(perfluoroalkyl)tetrahydropyran-3-one (12a), as a pure sample of an approximately 1:1 mixture of the cis and trans isomers in good to excellent yield. Just like perfluoroalkylation of 1a, vinyl ether 11a appeared to afford the corresponding addition product 12a in yields decreasing with increasing length of the perfluoroalkyl chain (see Figure 2).…”

Section: Exploratory Experiments Based On 1amentioning

confidence: 99%

“…In order to get an impression of the reactivity exhibited by vinyl ethers 1 under the reaction conditions employed by Zhu and Li, [7] various exploratory experiments were performed with the simplest representative of 1, namely (E)-4,5,5-triethoxypent-3-en-1-ol (1a). Three interesting sets of 4-Perfluoroalkylated Tetrahydropyran Derivatives results emerged.…”

Section: Exploratory Experiments Based On 1amentioning

confidence: 99%

“…The synthetic approach involves perfluoroalkylation by addition of a perfluoroalkyl iodide (R F I) to an alkene promoted by a radical initiator. Such reactions can be performed under a variety of conditions, [5][6][7] but we settled for a protocol applied successfully by Zhu and Li. [7] When their methodology was adopted we were able to develop reaction conditions that allowed selective conversion of 1-substituted (E)-4,5,5-triethoxypent-3-en-1-ol derivatives (1, Figure 1), [8] easily available from 3,3,4,4-tetraethoxybut-1-yne (TEB) as described in the literature, [9] to perfluoroalkylated derivatives of both tetrahydrofuran and tetrahydropyran.…”

Section: Introductionmentioning

confidence: 99%

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Preparation of 2‐Ethoxy‐3‐hydroxy‐4‐(perfluoroalkyl)tetrahydropyran Derivatives from Substituted 4‐Ethoxybut‐3‐en‐1‐ols

Valdersnes

Sydnes

2009

Eur J Org Chem

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A number of 1‐substituted and 1,1‐disubstituted (E)‐4,5,5‐triethoxypent‐3‐en‐1‐ols (1) have been converted to perfluoroalkylated tetrahydrofurans and tetrahydropyrans in a selective fashion by 1‐iodoperfluoroalkane addition under radical conditions using sodium dithionite (Na2S2O4) as radical initiator. Direct perfluoroalkylation of 1 gave the former products only, and the yields were moderate (50–75 %), but when 1 was converted to corresponding 6‐substituted and 6,6‐disubstituted 2,3‐diethoxy‐5,6‐dihydro‐2H‐pyrans before perfluoroalkylation was carried out, the transformation turned out to be significantly more successful and afforded, as the only product, 6‐substituted and 6,6‐disubstituted 2‐ethoxy‐4‐(perfluoroalkyl)tetrahydropyran‐3‐ones in 77–100 % yield as stereoisomeric mixtures. Subsequent reduction of the keto group with sodium borohydride in ethanol was uneventful and completed the syntheses of a range of 4‐perfluorobutylated tetrahydropyran derivatives; the yields in this step were in the 81–94 % range. The best result was obtained with (E)‐2‐methyl‐5,6,6‐triethoxyhex‐4‐en‐2‐ol which was converted to a diastereoisomeric mixture of 2‐ethoxy‐6,6‐dimethyl‐4‐(perfluorobutyl)tetrahydropyran‐3‐ol in 85 % yield in three steps. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Formation of CC Bonds: Sections 14.1 ‐ 14.6

Wong¹

2002

Enzyme Catalysis in Organic Synthesis

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The aldol reaction is one of the most powerful methods for carbon-carbon bond formation, and its catalytic asymmetric variants have great potential in contemporary organic synthesis ['I. Aldolases are enzymes which catalyze reversible and irreversible asymmetric aldol condensations in r~ature[~-~], via one of two distinct reaction mechanisms 1 ' 1 . Type I aldolases activate the donor/nucleophilic substrate via Schiff base formation with an active-site lysine residue. These enzymes are predominantly found in animals and higher plants, and do not require metal cofactors. Type I1 aldolases activate both donor and acceptor substrates via chelation to an active-site Zn", and are found mainly in microorganisms. Aldolases can be conveniently classified into groups according to their natural donor substrates, i. e. dihydroxyacetone phosphate (DHAP), pyruvate/phosphoenol pyruvate (PEP), glycine, acetaldehyde, and a small number of other molecules. The ability of aldolases to accept a variety of unnatural acceptor substrates, and to generate new stereocenters of known absolute and relative stereochemistry reliably, has made them powerful tools for asymmetric synthesis.FDP aldolase catalyzes the reversible aldol addition reaction of DHAP and Dglyceraldehyde 3-phosphate (D-G~Y 3-P) to form D-FDP (Fig. 14.1-1). The equilibrium constant for this reaction has a value of -lo4 M-' in favor of FDP formation. The enzyme has been isolated from a variety of eukaryotic and prokaryotic sources, both in type I and type I1 forms [7-211. Generally, the type I FDP aldolases exist as tetramers (M. W. -160 KDa), while the type I1 enzymes are dimers (M. W. -80 KDa). For the

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Synthesis of perfluoroalkylated sugars catalyzed by rabbit muscle aldolase (RAMA)

Cited by 14 publications

References 17 publications

C−C Bond-Forming Lyases in Organic Synthesis

C−C Bond-Forming Lyases in Organic Synthesis

Preparation of 2‐Ethoxy‐3‐hydroxy‐4‐(perfluoroalkyl)tetrahydropyran Derivatives from Substituted 4‐Ethoxybut‐3‐en‐1‐ols

Formation of CC Bonds: Sections 14.1 ‐ 14.6

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