methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-deoxy-α-D-arabino-hexopyranosyl)-α-D-glucopyranoside | 117841-70-0

分子结构分类

有机化合物 - 有机氧化合物

中文名称

——

中文别名

——

英文名称

methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-deoxy-α-D-arabino-hexopyranosyl)-α-D-glucopyranoside

英文别名

methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl)-α-D-glucopyranoside；methyl (3,4,6-tri-O-benzyl-2-deoxy-α-D-glucopyranosyl)-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl (3,4,6-tri-O-benzyl-2-deoxy-α-D-arabino-hexopyranosyl)-(1->6)-(2,3,4-tri-O-benzyl-α-D-glucopyranoside)；methyl 2,3,4-tri-O-benzyl-6-O-(2-deoxy-3,4,6-tri-O-benzyl-α-D-glucopyranosyl)-α-D-glucopyranoside；Bn(-3)[Bn(-4)][Bn(-6)]2-deoxy-D-araHex(a1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；(2R,3R,4S,5R,6S)-2-[[(2S,4R,5S,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxymethyl]-6-methoxy-3,4,5-tris(phenylmethoxy)oxane

methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-deoxy-α-D-arabino-hexopyranosyl)-α-D-glucopyranoside化学式

CAS

117841-70-0

化学式

C₅₅H₆₀O₁₀

mdl

——

分子量

881.075

InChiKey

SPRFHHRASDESNT-IOZXUVSISA-N

BEILSTEIN

——

EINECS

——

物化性质

沸点：

898.7±65.0 °C(Predicted)
密度：

1.22±0.1 g/cm3(Predicted)

计算性质

辛醇/水分配系数(LogP)：

8.4
重原子数：

65
可旋转键数：

23
环数：

8.0
sp3杂化的碳原子比例：

0.35
拓扑面积：

92.3
氢给体数：

0
氢受体数：

10

上下游信息

上游原料

中文名称	英文名称	CAS号	化学式	分子量
甲基2,3,4-三-O-苄基-α-D-吡喃葡萄糖苷	methyl 2,3,4-tri-O-benzyl-D-glucopyranoside	53008-65-4	C₂₈H₃₂O₆	464.558
——	(2S,3S,4R,5R,6R)-2-Allyloxy-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-ol	97576-68-6	C₃₀H₃₄O₆	490.596
——	methyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside	——	C₂₈H₃₀O₆	462.543
3,4,6-三-氧-苄基-2-脱氧-D-吡喃葡萄糖	3,4,6-tri-O-benzyl-2-deoxy-D-glucopyranose	160549-11-1	C₂₇H₃₀O₅	434.532
——	Thiobenzoic acid O-[(2S,3S,4S,5R,6R)-4,5-bis-benzyloxy-6-benzyloxymethyl-2-((2R,3R,4S,5R,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-ylmethoxy)-tetrahydro-pyran-3-yl] ester	207293-00-3	C₆₂H₆₄O₁₁S	1017.25
——	Thiobenzoic acid O-((2S,3S,4S,5R,6R)-2-allyloxy-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl) ester	207292-92-0	C₃₇H₃₈O₆S	610.771
甲基2,3,4-三-O-苄基-6-O-三苯甲基-ALPHA-D-吡喃葡萄糖苷	methyl 2,3,4-tri-O-benzyl-6-O-trityl-α-D-glucopyranoside	18685-19-3	C₄₇H₄₆O₆	706.879
——	3,4,6-Tri-O-benzyl-2-deoxy-α-D-glucopyranosyl trichloroacetamidate	220284-26-4	C₂₉H₃₀Cl₃NO₅	578.92
——	2-((2S,4R,5S,6R)-4,5-Bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-yloxymethyl)-benzoic acid	532959-22-1	C₃₅H₃₆O₇	568.667
——	O-[(2R,3S,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] benzenecarbothioate	207292-94-2	C₃₆H₃₄Cl₃NO₆S	715.094
甲基-6-O-三苯基甲基-alpha-D-吡喃葡萄糖苷	methyl 6-O-trityl-α-D-glucopyranoside	18311-26-7	C₂₆H₂₈O₆	436.505
——	2-((2S,4R,5S,6R)-4,5-Bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-2-yloxymethyl)-benzoic acid benzyl ester	532959-21-0	C₄₂H₄₂O₇	658.791
alpha-甲基葡萄糖甙	methyl-alpha-D-glucopyranoside	97-30-3	C₇H₁₄O₆	194.185
β-D-葡萄糖五乙酸酯	β-D-glucose pentaacetate	604-69-3	C₁₆H₂₂O₁₁	390.344
——	3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hexopyranosyl benzyl phthalate	779352-72-6	C₄₂H₄₀O₈	672.775
——	3,4,6-Tri-O-benzyl-2-deoxy-α-D-glucopyranosyl fluoride	163916-60-7	C₂₇H₂₉FO₄	436.523

反应信息

作为反应物：

描述：

methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-deoxy-α-D-arabino-hexopyranosyl)-α-D-glucopyranoside 在 palladium on activated charcoal 氢气作用下，以甲醇为溶剂，反应 3.0h，以95%的产率得到(2R,3S,4S,5R,6S)-2-((2S,4R,5S,6R)-4,5-Dihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yloxymethyl)-6-methoxy-tetrahydro-pyran-3,4,5-triol

参考文献：

名称：

Chemical mapping of the active site of the glucoamylase ofAspergillus niger

摘要：

最近开发的一种技术用于探测凝集素和抗体的结合位点，以建立与寡糖结合中涉及的表位的结构，用于研究酶葡萄糖酶对甲基α-异麦芽糖的结合。该过程涉及确定对水解动力学的影响，包括每个七个羟基的单去氧和单-O-甲基化，以获得活化自由能的差异变化ΔΔG^≠的估计。如预期的那样，根据先前的发表，OH-4（还原单元）、OH-4'或OH-6'的脱氧和O-甲基化强烈阻碍了水解，而OH-2的置换或C-1的结构变化几乎不影响动力学。OH-3的置换导致ΔΔG^≠增加了2.1和1.9 kcal/mol。相比之下，OH-2'或OH-3'的脱氧导致ΔΔG^≠增加较小（0.96和0.52 kcal/mol），而单-O-甲基化导致了对激活复合物形成的严重位阻。脱氧的相对较弱影响表明，羟基被水分子取代，从而通过提供有效的互补性参与结合。甲基α-异麦芽糖被对接到X射线晶体结构的结合位点，分辨率为2.4 Å的复合物与抑制剂阿卡波糖。找到了与蛋白质无位阻相互作用的适合，其中甲基α-葡萄糖吡喃糖单元处于正常的4C1构象，另一个葡萄糖单元接近半椅构象，其间单元片段由扭转角度定义[Formula: see text]该模型提供了一个氢键网络，似乎很好地代表了由葡萄糖酶与麦芽糖和异麦芽糖形成的激活复合物，因为这些结构似乎为酶提供的特异性和催化提供了合理的基础。关键词：甲基α-异麦芽糖的单去氧和单-O-甲基衍生物，酶结合结构域，葡萄糖酶的功能，活化自由能的差异变化，氢键网络的特性。

DOI：

10.1139/v96-036
作为产物：

描述：

3,4,6-三-氧-苄基-2-脱氧-D-吡喃葡萄糖在 4 A molecular sieve 、 lithium perchlorate 、 potassium carbonate 、 cesium fluoride 作用下，以乙醚、二氯甲烷为溶剂，反应 72.0h，生成 methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-deoxy-α-D-arabino-hexopyranosyl)-α-D-glucopyranoside

参考文献：

名称：

Schene, Heidrun; Waldmann, Herbert, Chemical Communications, 1998, # 24, p. 2759 - 2760

摘要：

DOI：

点击查看最新优质反应信息

文献信息

An Air- and Water-Stable Iodonium Salt Promoter for Facile Thioglycoside Activation

作者：An-Hsiang Adam Chu、Andrei Minciunescu、Vittorio Montanari、Krishna Kumar、Clay S. Bennett

DOI：10.1021/ol5004059

日期：2014.3.21

iodonium salt phenyl(trifluoroethyl)iodonium triflimide is shown to activate thioglycosides for glycosylation at room temperature. Both armed and disarmed thioglycosides rapidly undergo glycosylation in 68–97% yield. The reaction conditions are mild and do not require strict exclusion of air and moisture. The operational simplicity of the method should allow experimentalists with a limited synthetic background

空气和水稳定的碘鎓盐苯基（三氟乙基）碘鎓三氟甲磺酰亚胺在室温下可激活硫代糖苷以进行糖基化。武装和解除武装的硫糖苷都以 68-97% 的产率迅速进行糖基化。反应条件温和，不需要严格排除空气和水分。该方法的操作简单性应该允许具有有限合成背景的实验者构建糖苷键。
TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals

作者：Mei-Yuan Hsu、Yi-Pei Liu、Sarah Lam、Su-Ching Lin、Cheng-Chung Wang

DOI：10.3762/bjoc.12.164

日期：——

The thio-additions of glycals were efficiently promoted by a stoichiometric amount of trimethylsilyl bromide (TMSBr) to produce S-2-deoxyglycosides under solvent-free conditions in good to excellent yields. In addition, with triphenylphosphine oxide as an additive, the TMSBr-mediated direct glycosylations of glycals with a large range of alcohols were highly α-selective.

甘露糖醛酸盐的硫加成反应可以在无溶剂条件下高效地通过等物量的溴化三甲基硅(TMSBr)催化产生良好至优异收率的S-2-脱氧糖苷。此外，加入三苯基膦氧化物作为添加剂，TMSBr介导的甘露糖醛酸盐与多种醇类的直接糖基化反应具有高度α-选择性。
A 3,4-<i>trans</i>-Fused Cyclic Protecting Group Facilitates α-Selective Catalytic Synthesis of 2-Deoxyglycosides

作者：Edward I. Balmond、David Benito-Alifonso、Diane M. Coe、Roger W. Alder、Eoghan M. McGarrigle、M. Carmen Galan

DOI：10.1002/anie.201403543

日期：2014.7.28

disaccharides or glycoconjugates with high α‐selectivity and yields (77–97 %) using a trans‐fused cyclic 3,4‐O‐disiloxane protecting group and TsOH⋅H2O (1 mol %) as a catalyst. Control of the anomeric selectivity arises from conformational locking of the intermediate oxacarbenium cation. Glucals outperform rhamnals because the C6 side‐chain conformation augments the selectivity.

已经开发出一种实用的方法，使用反式稠合环状 3,4-O-二硅氧烷保护基团和 TsOH⋅H 2 O ，将葡糖和鼠李糖转化为具有高α-选择性和产率（77-97%）的二糖或糖缀合物（ 1 mol%) 作为催化剂。异头选择性的控制来自中间氧杂碳鎓阳离子的构象锁定。Glucals 优于鼠李糖醇，因为 C6 侧链构象增强了选择性。
Glycosylation Reactions Using Phenyl(trifluoroethyl)iodonium Salts

申请人：Trustees of Tufts College

公开号：US20150099870A1

公开（公告）日：2015-04-09

Provided are methods for the preparation of glycosylation products, including those represented by formula I: Sugar-O—R′ I comprising the step of combining R′—OH, a glycosyl sulfide glycosyl donor (“thioglycoside donor”), a hypervalent iodine alkyl-transfer activating reagent, and a base. In an embodiment, the hypervalent iodine alkyl-transfer activating reagent is (phenyl(trifluoroethyl)iodonium triflimide).

提供了制备糖基化产物的方法，包括由式I表示的那些：糖-O—R′ I 包括将R′—OH、糖基硫醚糖基供体（“硫代糖苷供体”）、高价碘烷基转移活化试剂和碱结合的步骤。在一种实施例中，高价碘烷基转移活化试剂为（苯基(三氟乙基)碘三氟甲磺酰胺）。
Cooperative Brønsted Acid-Type Organocatalysis for the Stereoselective Synthesis of Deoxyglycosides

作者：Carlos Palo-Nieto、Abhijit Sau、Ryan Williams、M. Carmen Galan

DOI：10.1021/acs.joc.6b02498

日期：2017.1.6

α-stereoselective synthesis of deoxyglycosides using cooperative Brønsted acid-type organocatalysis has been developed. The method is tolerant of a wide range of glycoside donors and acceptors, and its versatility is exemplified in the one-pot synthesis of a trisaccharide. Mechanistic studies suggest that thiourea-induced acid amplification of the chiral acid via H-bonding is key for the enhancement

已经开发了一种使用布朗斯台德酸型有机催化协同催化α-立体选择性合成脱氧糖苷的实用方法。该方法耐受多种糖苷供体和受体，并且其多功能性在三糖的一锅法合成中得到了例证。机理研究表明，硫脲通过氢键引起的手性酸的酸扩增是提高反应速率和产率的关键，而立体控制则取决于酸的手性。