Enzymatic β-glycosidation of primary alcohols

Kurashima, Katsumi; Fujii, Mikio; Ida, Yoshiteru; Akita, Hiroyuki

doi:10.1016/s1381-1177(03)00168-1

Cited by 31 publications

(25 citation statements)

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“…Enzymatic synthesis of n-hexyl b-D-glucopyranoside (1) 5) and 6-hydroxyhexyl-b-D-glucopyranoside (6) 6) using 4-nitrophenyl b-D-glucopyranoside as a glycosyl donor was reported previously by us, while direct b-glycosidation using a large amount of 1,6-hexanediol is reported to give a 6-hydroxyhexyl-b-D-glucopyranoside (6) in 61% yield. 4) Those reports are promising for the improved synthesis of n-hexyl b-D-glucopyranoside (1) and its application to the total synthesis of the natural congener (2).…”

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confidence: 85%

“…4) Those reports are promising for the improved synthesis of n-hexyl b-D-glucopyranoside (1) and its application to the total synthesis of the natural congener (2). On the other hand, we reported the effectiveness of immobilization of b-glucosidase (EC 3.2.1.21) from almonds with a photocross-linkable resin prepolymer (ENTP-4000) in the direct b-glucosidation between D-glucose (3) and 1,8-octanediol (5). 7) Then we examined the direct b-glucosidation between D-glucose (3) and 1-hexanol (4) or/and 1,6-hexanediol (5).…”

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confidence: 99%

“…On the other hand, we reported the effectiveness of immobilization of b-glucosidase (EC 3.2.1.21) from almonds with a photocross-linkable resin prepolymer (ENTP-4000) in the direct b-glucosidation between D-glucose (3) and 1,8-octanediol (5). 7) Then we examined the direct b-glucosidation between D-glucose (3) and 1-hexanol (4) or/and 1,6-hexanediol (5). Immobilization of b-D-glucosidase from almonds on the photocross-linkable resin prepolymer (ENTP-4000) was carried out following the reported procedure.…”

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confidence: 99%

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Chemoenzymatic Synthesis of n-Hexyl and O-.BETA.-D-Xylopyranosyl-(1.RAR.6)-.BETA.-D-glucopyranosides

Kishida

Nishiuchi

Kato

et al. 2004

CHEMICAL & PHARMACEUTICAL BULLETIN

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The Chinese natural medicine "Si Lie Hong Jing Tian" prepared from the underground part of Rhodiola (R.) quadrifida (PALL.) FISCH. et MEY., has been prescribed for hemostatic, antibechic, and tonic purposes in traditional Chinese preparations and used as an endermic liniment for burns and contusions. n-Hexyl b-D-glucopyranoside (1) was isolated as one of chemical constituents of R. quadrifida by Yoshikawa et al.1) and reported to increase blood pressure.2) was isolated from the dried roots of Rehmannia glutinosa LIBOSH. var. purpurea MAKINO.3) In this paper, we describe the synthesis of n-hexyl b-D-glucopyranoside (1) and its natural congener (2) based on the selective b-glycosidation between the nonprotected D-glucose (3) and primary alcohols such as n-hexanol (4) and 1,6-hexanediol (5) catalyzed by the immobilized b-glucosidase (EC 3.2.1.21) from almonds. Retrosynthetically, the synthesis of 2 can be achieved by the coupling reaction of the protected n-hexyl b-D-glucopyranoside congener and the protected b-D-xylosyl congener.Enzymatic b b-Glycosidation In case of the direct b-glycosidation between D-glucose (3) and primary alcohols using b-glucosidase (EC 3.2.1.21) from almonds under thermodynamic conditions, a high concentration of alcohol or a medium with low water activity is reported to be effective. 4)Enzymatic synthesis of n-hexyl b-D-glucopyranoside (1) 5) and 6-hydroxyhexyl-b-D-glucopyranoside (6) 6) using 4-nitrophenyl b-D-glucopyranoside as a glycosyl donor was reported previously by us, while direct b-glycosidation using a large amount of 1,6-hexanediol is reported to give a 6-hydroxyhexyl-b-D-glucopyranoside (6) in 61% yield. 4) Those reports are promising for the improved synthesis of n-hexyl b-D-glucopyranoside (1) and its application to the total synthesis of the natural congener (2). On the other hand, we reported the effectiveness of immobilization of b-glucosidase (EC 3.2.1.21) from almonds with a photocross-linkable resin prepolymer (ENTP-4000) in the direct b-glucosidation between D-glucose (3) and 1,8-octanediol (5).7) Then we examined the direct b-glucosidation between D-glucose (3) and 1-hexanol (4) or/and 1,6-hexanediol (5). Immobilization of b-D-glucosidase from almonds on the photocross-linkable resin prepolymer (ENTP-4000) was carried out following the reported procedure. 7)When a large amount of 1-hexanol (4, 23.4 eq) was used as an acceptor for D-glucose (3) in the presence of b-glucosidase or the immobilized b-glucosidase, a low yield of nhexyl b-D-glucopyranoside (1) (entry 1 in Table 1; 13.5% yield, entry 2 in Table 1; 9.4% yield) was obtained. When the same b-glucosidation was carried out using the recovered immobilized enzyme, the yield of 1 was almost the same as in entry 2 in Table 1 (entry 3 in Table 1). When a large amount of 1,6-hexanediol (5; 25.0 eq) was employed for bglucosidation using the native enzyme and the immobilized enzyme, the yield of 6 was fairly high (entry 4 in Table 1; 67.8% yield, entry 5 in Table 1; 61.4% yield). The recovered enzyme was also found to...

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Section: )mentioning

confidence: 85%

Section: )mentioning

confidence: 99%

Section: )mentioning

confidence: 99%

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Chemoenzymatic Synthesis of n-Hexyl and O-.BETA.-D-Xylopyranosyl-(1.RAR.6)-.BETA.-D-glucopyranosides

Kishida

Nishiuchi

Kato

et al. 2004

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…7,8) The b-glucosidase (EC 3.2.1.21) from almonds was purchased from Sigma Chemical Co. (G-0395, 2.5-3.4 U/mg), and 4-nitrophenyl b-D-glucopyranoside (5) as a glycosyl donor was chosen from either several kinds of phenyl b-D-glucopyranoside congeners or cellobiose. 7) In continuation of our studies on the enzymatic b-glucosidation of alcohols, we now report the enzymatic b-glucosidation of twenty-one kinds of alcohols, including primary alcohols, secondary alcohols and 1,w-alkanediol.…”

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Simple Synthesis of .BETA.-D-Glycopyranosides Using .BETA.-Glycosidase from Almonds

et al. 2004

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There are many b-D-glucopyranosides possessing a primary alcohol moiety as an aglycone part in nature. The development of stereoselective methods for the synthesis of glycosidic linkages presents a considerable challenge to synthetic chemists.1,2) Although well-developed chemical synthesis of the glycosidic structure is increasingly being established, several steps of selective protection, activation and coupling using a metal catalyst are necessary in their process. This problem in chemical synthesis has promoted the development of enzymatic approaches. Lipase-catalyzed synthesis of acyl sugar has been reported, 3) whereas much less is known about glycosidase-catalyzed synthesis of alkyl glycosides.4) Glycosidases are responsible for the catalytic hydrolysis of the glycosidic linkage and are increasingly being used in carbohydrate synthesis. For example, b-glucosidase catalyzes the stereospecific hydrolytic cleavage of the b-glucosidic bond in substrate (1) to give glucose (2) (Chart 1, path a). Meanwhile, the reaction of b-D-glucopyranoside (1) and a nucleophile such as an alcohol is reported to afford a new glucopyranoside (3) exclusively with the b-configuration (Chart 1, path b). 5)In the latter case, serine congeners were used as an acceptor alcohol. The success of the glycosidic bond formation requires the reactive intermediate (enzyme bound glycosyl cation) to be trapped faster by the glycosyl acceptor than by water. We are interested in this transglycosylation reaction, since alcohols as the glucosyl acceptor are better bound at the active site than water. There are two approaches to optimizing the product yield from a given glycosidase in enzymatic glycoside synthesis, i.e., the use of either a high donor or high acceptor concentration.6) High concentrations of both are usually impractical due to solubility limitation. High donor concentrations are only practical if the donor is cheap, such as glucose. High acceptor concentrations are practical if the acceptor is cheap or can be recovered from the reaction mixture. For the purpose of the synthesis of naturally occurring b-D-glucopyranosides, it is desirable to use an equal portion of both the glycosyl donor and the acceptor alcohol from a synthetic point of view. We reported that screening experiments in respect of the enzymes, glycosyl donors in phosphate buffer solution in order to find the best reaction conditions of b-glucosidation of primary alcohols were carried out. 7)The effective enzyme and glycosyl donor, respectively, for the synthesis of benzyl b-D-glucopyranoside (4) as a model transglycosylation appeared to be b-glucosidase (EC 3.2.1.21) from almonds and 4-nitrophenyl b-D-glucopyranoside (5). a Enzymes and Pharmaceuticals Research Laboratory, Godo Shusei Co., Ltd.; 250 Nakahara, Kamihongo, Matsudo, Chiba 271-0064, Japan: b School of Pharmaceutical Sciences, Showa University; 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan: and c School of Pharmaceutical Sciences, Toho University; 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan. R...

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“…Meanwhile, the synthesis of 1 using 4-nitrophenyl b-D-glucopyranoside as a glycosyl donor was reported previously by us. 8) On the other hand, we reported the effectiveness of immobilization of b-glucosidase (EC 3.2.1.21) from almonds with a photocross-linkable resin prepolymer (ENTP-4000) in the direct b-glucosidation of 1,8-octanediol with D-glucose (5). 9) Then we examined the direct b-glucosidation of benzyl alcohol with D-glucose (5) using the reported immobilized b-glucosidase (EC 3.2.1.21) 9) from almonds.…”

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Chemoenzymatic Synthesis of Naturally Occurring Benzyl 6-O-Glycosyl-.BETA.-D-glucopyranosides

Kawahara

Fujii

Kato

et al. 2005

CHEMICAL & PHARMACEUTICAL BULLETIN

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Enzymatic β-glycosidation of primary alcohols

Cited by 31 publications

References 18 publications

Chemoenzymatic Synthesis of n-Hexyl and O-.BETA.-D-Xylopyranosyl-(1.RAR.6)-.BETA.-D-glucopyranosides

Chemoenzymatic Synthesis of n-Hexyl and O-.BETA.-D-Xylopyranosyl-(1.RAR.6)-.BETA.-D-glucopyranosides

Simple Synthesis of .BETA.-D-Glycopyranosides Using .BETA.-Glycosidase from Almonds

Chemoenzymatic Synthesis of Naturally Occurring Benzyl 6-O-Glycosyl-.BETA.-D-glucopyranosides

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