(2R,4aR,6S,6aR,9aR,9bS)-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazol-8(6H)-one | 1280531-26-1

分子结构分类

有机化合物 - 有机硫化合物 - 硫醚类

中文名称

——

中文别名

——

英文名称

(2R,4aR,6S,6aR,9aR,9bS)-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazol-8(6H)-one

英文别名

——

(2R,4aR,6S,6aR,9aR,9bS)-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazol-8(6H)-one化学式

CAS

1280531-26-1

化学式

C₂₀H₁₉NO₅S

mdl

——

分子量

385.441

InChiKey

UIWYHDKPZSYJHI-UPGMHYFXSA-N

BEILSTEIN

——

EINECS

——

物化性质

沸点：

652.8±55.0 °C(Predicted)
密度：

1.42±0.1 g/cm3(Predicted)

计算性质

辛醇/水分配系数(LogP)：

3.09
重原子数：

27.0
可旋转键数：

3.0
环数：

5.0
sp3杂化的碳原子比例：

0.35
拓扑面积：

66.02
氢给体数：

1.0
氢受体数：

6.0

上下游信息

下游产品

中文名称	英文名称	CAS号	化学式	分子量
——	[(3aR,4R,6R,7S,7aR)-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-3,3a,4,6,7,7a-hexahydropyrano[3,4-d][1,3]oxazol-7-yl] acetate	1280531-38-5	C₂₂H₂₃NO₆S	429.494
——	(3aR,4S,6R,7S,7aR)-6-((benzyloxy)methyl)-2-oxo-4-(phenylthio)hexahydro-4H-pyrano[3,4-d]oxazol-7-yl acetate	1280531-21-6	C₂₂H₂₃NO₆S	429.494
——	methyl (2R,4aR,6S,6aR,9aR,9bS)-8-oxo-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazole-7(8H)-carboxylate	1280531-27-2	C₂₂H₂₁NO₇S	443.477
——	(3aR,4S,6R,7S,7aR)-7-hydroxy-6-(phenylmethoxymethyl)-4-phenylsulfanyl-3,3a,4,6,7,7a-hexahydropyrano[3,4-d][1,3]oxazol-2-one	371123-29-4	C₂₀H₂₁NO₅S	387.456
——	2-((2R,4aR,6S,6aR,9aR,9bS)-8-oxo-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazol-7(8H)-yl)acetonitrile	1537195-28-0	C₂₂H₂₀N₂O₅S	424.477
——	2,2,2-trichloroethyl (2R,4aR,6S,6aR,9aR,9bS)-8-oxo-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazole-7(8H)-carboxylate	1537195-34-8	C₂₃H₂₀Cl₃NO₇S	560.839
——	benzyl (2R,4aR,6S,6aR,9aR,9bS)-8-oxo-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazole-7(8H)-carboxylate	1537195-38-2	C₂₈H₂₅NO₇S	519.575
——	phenyl N-benzyl-2-amino-4,6-O-benzylidene-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	910805-49-1	C₂₇H₂₅NO₅S	475.565
——	(2R,4aR,6S,6aR,9aR,9bS)-7-(4-methoxybenzyl)-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazol-8(6H)-one	1357473-38-1	C₂₈H₂₇NO₆S	505.591
——	methyl (3aR,4R,6R,7S,7aR)-7-acetyloxy-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazole-3-carboxylate	1280531-40-9	C₂₄H₂₅NO₈S	487.53
——	methyl (3aR,4S,6R,7S,7aR)-7-acetyloxy-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazole-3-carboxylate	1280531-28-3	C₂₄H₂₅NO₈S	487.53
——	phenyl N-allyoxycarbonyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-α-D-glucopyranoside	1537194-92-5	C₂₆H₂₇NO₈S	513.568
——	phenyl N-allyoxycarbonyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-91-4	C₂₆H₂₇NO₈S	513.568
——	methyl (3aR,4S,6R,7S,7aR)-6-((benzyloxy)methyl)-7-hydroxy-2-oxo-4-(phenylthio)tetrahydro-4H-pyrano[3,4-d]oxazole-3(2H)-carboxylate	1280531-29-4	C₂₂H₂₃NO₇S	445.493
——	phenyl N-methoxyethyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-90-3	C₂₅H₂₇NO₈S	501.557
——	phenyl N-cyanomethyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-α-D-glucopyranoside	1537194-89-0	C₂₄H₂₄N₂O₆S	468.53
——	phenyl N-cyanomethyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-88-9	C₂₄H₂₄N₂O₆S	468.53
——	phenyl N-trichloroethyloxycarbonyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-95-8	C₂₅H₂₄Cl₃NO₈S	604.892
——	phenyl N-trichloroethyloxycarbonyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-α-D-glucopyranoside	1537194-96-9	C₂₅H₂₄Cl₃NO₈S	604.892
——	phenyl N-benzyloxycarbonyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-α-D-glucopyranoside	1537194-94-7	C₃₀H₂₉NO₈S	563.628
——	phenyl N-benzyloxycarbonyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-93-6	C₃₀H₂₉NO₈S	563.628
——	2,2,2-trichloroethyl (3aR,4S,6R,7S,7aR)-6-((benzyloxy)methyl)-7-hydroxy-2-oxo-4-(phenylthio)tetrahydro-4H-pyrano[3,4-d]oxazole-3(2H)-carboxylate	1537195-35-9	C₂₃H₂₂Cl₃NO₇S	562.855
——	[(3aR,4S,6R,7S,7aR)-3-acetyl-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-7-yl] acetate	1280531-23-8	C₂₄H₂₅NO₇S	471.531
——	[(3aR,4R,6R,7S,7aR)-3-acetyl-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-7-yl] acetate	1280531-39-6	C₂₄H₂₅NO₇S	471.531
——	(3aR,4S,6R,7S,7aR)-3-acetyl-6-((benzyloxy)methyl)-7-hydroxy-4-(phenylthio)tetrahydro-4H-pyrano[3,4-d]oxazol-2(3H)-one	1332836-66-4	C₂₂H₂₃NO₆S	429.494
——	[(3aR,4S,6R,7S,7aR)-3-benzyl-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-7-yl] acetate	1140972-37-7	C₂₉H₂₉NO₆S	519.618
——	[(3aR,4R,6R,7S,7aR)-3-benzyl-2-oxo-6-(phenylmethoxymethyl)-4-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-7-yl] acetate	1140972-38-8	C₂₉H₂₉NO₆S	519.618
——	phenyl N-o-nitrobenzyl-2-amino-4,6-O-benzylidene-2-N,3-O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1352653-29-2	C₂₇H₂₄N₂O₇S	520.563
——	phenyl N-benzyl-2-amino-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	910805-50-4	C₂₇H₂₇NO₅S	477.581
——	phenyl N-4-methoxybenzyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-α-D-glucopyranoside	1537194-85-6	C₃₀H₃₁NO₇S	549.645
——	phenyl N-4-methoxybenzyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-84-5	C₃₀H₃₁NO₇S	549.645
——	(3aR,4S,6R,7S,7aR)-6-((benzyloxy)methyl)-7-hydroxy-3-(4-methoxybenzyl)-4-(phenylthio)tetrahydro-4H-pyrano[3,4-d]oxazol-2(3H)-one	1537195-27-9	C₂₈H₂₉NO₆S	507.607
——	phenyl N-2-nitrobenzyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-α-D-glucopyranoside	1537194-87-8	C₂₉H₂₈N₂O₈S	564.616
——	phenyl N-2-nitrobenzyl-2-amino-4-O-acetyl-6-O-benzyl-2,3-N,O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1537194-86-7	C₂₉H₂₈N₂O₈S	564.616
——	phenyl N-o-nitrobenzyl-2-amino-6-O-benzyl-2-N,3-O-carbonyl-2-deoxy-1-thio-β-D-glucopyranoside	1352653-34-9	C₂₇H₂₆N₂O₇S	522.579

反应信息

作为反应物：

描述：

(2R,4aR,6S,6aR,9aR,9bS)-2-phenyl-6-(phenylthio)hexahydro-[1,3]dioxino[4',5':5,6]pyrano[3,4-d]oxazol-8(6H)-one 在三乙基硅烷、三氟化硼乙醚作用下，以二氯甲烷为溶剂，生成 (3aR,4S,6R,7S,7aR)-7-hydroxy-6-(phenylmethoxymethyl)-4-phenylsulfanyl-3,3a,4,6,7,7a-hexahydropyrano[3,4-d][1,3]oxazol-2-one

参考文献：

名称：

吡喃糖苷的异构化反应的重要取代基效应：1,2-反式异构体的1,2-顺式氨基葡萄糖低聚体的异构化和合成机理

摘要：

在弱酸性条件下，含有2,3-反式氨基甲酸酯基团的氨基糖苷很容易从1,2-反式糖苷变为1,2-顺式异构体。氨基甲酸酯的N-取代基对异构化反应有显着影响。特别是，N-乙酰基促进了快速和完全的α-异构化。DFT计算的结果支持了由于各种N取代基引起的反应性差异。发现乙酰基羰基的接近异头位置的方向显着地促进了异构化反应的进行。通过利用该反应，可形成具有多个1,2-顺式的低聚氨基糖苷糖苷键是通过一个步骤从1,2-反式糖苷生成的。

DOI：

10.1002/chem.201303474

点击查看最新优质反应信息

文献信息

Endocyclic Cleavage in Glycosides with 2,3-<i>trans</i> Cyclic Protecting Groups

作者：Hiroko Satoh、Shino Manabe、Yukishige Ito、Hans P. Lüthi、Teodoro Laino、Jürg Hutter

DOI：10.1021/ja201024a

日期：2011.4.13

is proposed as a reaction mechanism for the anomerization from the β (1,2-trans) to the α (1,2-cis) configuration observed in glycosides carrying 2,3-trans cyclic protecting groups. This reaction occurs in the presence of a weak Lewis or Brønsted acid, while endocyclic cleavage (endocleavage) in typical glycosides was observed only when mediated by protic media or strong Lewis acids. To rationalize

提出了内环途径作为在携带 2,3-反式环状保护基团的糖苷中观察到的从 β（1,2-反式）到 α（1,2-顺式）构型异构化的反应机制。该反应在弱路易斯酸或布朗斯台德酸存在下发生，而典型糖苷中的环内裂解（内裂解）仅在质子介质或强路易斯酸介导时观察到。为了使这类化合物的行为合理化，使用量子力学 (QM) 计算和实验研究研究了内切的反应机制和促进因素。我们研究了携带 2,3-反式环状保护基团的硫糖苷的异构化反应，使用三氟化硼醚合物 (BF(3)·OEt(2)) 作为路易斯酸。估计的理论反应性，基于一个简单的模型来预测由稠环引起的应变的过渡态 (TS) 能量，非常接近通过内 CO 键断裂后沿 C1-C2 键旋转的 TS 搜索计算的 TS 能量。在预测的 TS 能量和实验反应性等级之间发现了极好的一致性。这一系列的计算和实验强烈支持内环而不是外环机制的优势。此外，这些研究表明内部应变是增强内切反应的主
Substituent effects in endocyclic cleavage–recyclization anomerization reaction of pyranosides

作者：Shino Manabe、Kazuyuki Ishii、Hiroko Satoh、Yukishige Ito

DOI：10.1016/j.tet.2011.09.059

日期：2011.12

Pyranosides with 2,3-trans carbamate or 2,3-trans carbonate groups are anomerized under mild acidic conditions via endocyclic cleavage reaction. In order to understand the nature of the anomerization reaction via the endocyclic cleavage recyclization process, the substituent effects at various positions were investigated. (C) 2011 Elsevier Ltd. All rights reserved.