methyl-3,6-anhydro-α-D-glucopyranoside | 13407-60-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-3,6-anhydro-α-D-glucopyranoside
• 英文别名: (1R,3S,4R,5S,8R)-3-methoxy-2,6-dioxabicyclo[3.2.1]octane-4,8-diol
• CAS: 13407-60-8
• 化学式: C₇H₁₂O₅
• 分子量: 176.169
• InChiKey: LYLSUYCOHWVOFS-OVHBTUCOSA-N

物化性质

• 熔点：
  108 °C
• 沸点：
  378.5±42.0 °C(Predicted)
• 密度：
  1.41±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  68.2
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl-3,6-anhydro-α-D-glucopyranoside 在 硫酸 、 水 作用下， 生成 3,6-脱水-D-葡萄糖
  参考文献：
  名称：

  148.碳水化合物硫酸酯。第二部分 从甲基己吡喃糖苷硫酸盐中分离出3：6-脱水甲基己糖苷

  摘要：

  DOI：

  10.1039/jr9410000830
• 作为产物：
  描述：

  methyl 2,3,4-tri-O-acetyl-α-D-glucopyranose 在 吡啶 、 甲醇 、 sodium hydroxide 、 sodium 作用下， 生成 methyl-3,6-anhydro-α-D-glucopyranoside
  参考文献：
  名称：

  Haworth et al., Journal of the Chemical Society, 1941, p. 88,97

  摘要：

  DOI：

文献信息

• Rhodium catalysed asymmetric hydroformylation with diphosphite ligands based on sugar backbones
  作者：Godfried J.H. Buisman、Marti E. Martin、Eric J. Vos、Angélique Klootwijk、Paul C.J. Kamer、Piet W.N.M. van Leeuwen

  DOI：10.1016/0957-4166(95)00068-z

  日期：1995.3

  used in the rhodium catalysed asymmetric hydroformylation of styrene. Enantioselectivities up to 64% have been obtained with stable hydridorhodium diphosphite dicarbonyl catalysts (HRhPP(CO)2). High regioselectivities (up to 97%) to the branched aldehyde were found at relatively mild reaction conditions (T = 25–40°C, 9–45 bar of syngas pressure). The solution structures of HRhPP(CO)2 catalysts have been

  从（2,2'-联苯-1,1'-二基）制备的手性二亚磷酸酯配体（PP），（4,4'，6,6'-四-吨-丁基-2,2'-联苯1 1,1'-二基），4,4'-二-吨-丁基-6,6'-二甲氧基-2,2'-联苯-1,1'-二基）和二（2-吨丁基，6-甲基苯基）} phosphorochloridites和糖骨架1,2- ö异亚丙基d呋喃木糖，甲基-2,3- ö异亚丙基α -D-吡喃甘露糖苷和（甲基-3,6-脱水）-α-D-甘露吡喃糖苷，α-D-吡喃葡萄糖苷和β-D-吡喃半乳糖苷}已用于铑催化的苯乙烯的不对称加氢甲酰化反应。使用稳定的亚磷酸氢二钠二羰基催化剂（HRhPP（CO）2）。在相对温和的反应条件下（T = 25–40°C，合成气压力为9–45 bar），发现对支链醛的区域选择性高（高达97％）。通过31 P和1 H NMR光谱研究了HRhPP（CO）2催化剂的溶液结构。二亚磷酸酯配体与铑中
• Oxaphosphoranylation of methyl α-<scp>D</scp>-glucopyranoside with diethoxytriphenylphosphorane. A highly stereoselective route to anhydropyranosides
  作者：Nita A. Eskew、Slayton A. Evans

  DOI：10.1039/c39900000706

  日期：——

  Diethoxytriphenylphosphorane (DTPP) efficiently oxaphosphoranylates methyl α-D-glucopyranoside (1) to afford two isomeric 1,3,2λ5-dioxaphospholanes (2 and 3); thermolysis of the mixture of intermediates (2) and (3) affords methyl 2,3-anhydro-α-D-allopyranoside (4) and methyl 3,4-anhydro-α-D-galactopyranoside (5); however, in the presence of lithium bromide (LiBr), thermolysis of (2) and (3) is regiospecific

  Diethoxytriphenylphosphorane（DTPP）有效地oxaphosphoranylates甲基α- d吡喃葡萄糖苷（1），得到两种异构体1,3,2λ 5 -dioxaphospholanes（2和3）; 将中间体（2）和（3）的混合物热解，得到甲基2,3-脱水-α - D-吡喃侧葡糖苷（4）和甲基3,4-脱水-α - D-吡喃侧吡喃糖苷（5）；但是，在溴化锂（LiBr）的存在下，（2）和（3）的热解具有区域特异性，仅提供别皮吡喃糖苷（4）。
• Studies Relevant to Ellagitannin Chemistry:  Highly Diastereoselective Intramolecular Biaryl Coupling in Bis(iodotrimethoxybenzoyl) Hexopyranose Derivatives
  作者：Dongcheng Dai、Olivier R. Martin

  DOI：10.1021/jo971722k

  日期：1998.10.1

  Internal biaryl coupling reactions of carbohydrate derivatives carrying two 2-iodo-3,4,5-trimethoxybenzoyl groups under Ullmann conditions were investigated. With substituents at positions 2,3 or 4,6 of a D-glucopyranoside, 2,3 of a D-mannopyranoside, and 3,4 of a D-galactopyranoside, the coupling was found to proceed with a very high degree of stereoselectivity, leading exclusively to the (S)-epimer of the resulting hexamethoxydiphenoyl residue from the D-gluco and D-galacto substrates, and to the (R)-epimer from the D-manno substrate. With substituents at positions 2,4 of D-glucopyranose derivatives in the C-1(4) conformation and at positions 5,6 of a D-glucofuranose derivative, the coupling proceeded efficiently but with modest stereoselectivity. Some deiodinated starting material was formed as a byproduct in all reactions. These results are relevant to ellagitannin chemistry in that they provide further understanding of the structural requirements for highly diastereoselective biaryl coupling within carbohydrate units. In addition, the efficient, complementary reactions of the D-manno and D-galacto substrates provide a method for the enantioselective synthesis of hexamethoxydiphenoic acid derivatives.
• Sugar nitrates. Part II. The preparation and reactions of some nitrates, sulphonates, sulphinates, and other esters of methyl 4 : 6-O-benzylidene-α-<scp>D</scp>-glucoside
  作者：John Honeyman、J. W. W. Morgan

  DOI：10.1039/jr9550003660

  日期：——
• Enantioselective hydrogenation of functionalized olefins catalyzed by Rh-chiral bidentatephosphite complexes
  作者：Qing-Lu Zhao、Xiao Miao、Lai-Lai Wang

  DOI：10.1016/j.tetasy.2012.12.001

  日期：2013.2

  A novel catalytic system for the hydrogenation of dimethyl itaconate has been developed by using rhodium-diphosphite complexes. These chiral diphosphite ligands were derived from glucopyranoside, D-mannitol derivatives, and binaphthyl or H-8-binaphthyl phosphochloridites. The ligands based on the methyl 3,6-anhydro-alpha-D-glucopyranoside backbone and (R)- and (S)-binaphthol and/or (R)- and (S)-2,2'-dihydroxy-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthol gave almost complete conversion of the dimethyl itaconate and both enantiomers of dimethyl 2-methylsuccinate with excellent enantioselectivities. The stereochemically matched combination of methyl 3,6-anhydro-alpha-D-glucopyranoside and H-8-(S)-binaphthyl in ligand 2,4-bis[(S)-1,1'-H-8-binaphthyl-2,2'-diyl]-phosphite} methyl 3,6-anhydro-alpha-D-glucopyranoside was essential to afford dimethyl 2-methylsuccinate with up to 98% ee. The sense of the enantioselectivity of products was predominantly determined by the configuration of the biaryl moieties of the ligands. An initial screening of [Rh(cod)(2)]BF4 with these ligands in the hydrogenation of (E)-2-(3-butoxy-4-methoxybenzylidene)-3-methylbutanoic acid was carried out. Good enantioselectivity (75% ee) and low yield for (R)-2-(3-butoxy-4-methoxybenzyl)-3-methylbutanoic acid were obtained. (C) 2012 Elsevier Ltd. All rights reserved.