(4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)benzene | 201232-86-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)benzene
• 英文别名: tert-butyl-[[(2R,3S,6S)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-phenyl-3,6-dihydro-2H-pyran-3-yl]oxy]-dimethylsilane
• CAS: 201232-86-2
• 化学式: C₂₄H₄₂O₃Si₂
• 分子量: 434.767
• InChiKey: LFVANEDDDRGLMY-FDFHNCONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.09
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)benzene 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以80%的产率得到(2,3-Dideoxy-α-D-erythro-hex-2-enopyranosyl)benzene
  参考文献：
  名称：

  Epoxidation and Bis-hydroxylation of C-Phenyl-∆2,3-glycopyranosides

  摘要：

  为了发展 C-芳基糖苷的合成，对 C-苯基-Δ2,3-吡喃糖苷进行了环氧化和顺式羟化反应。(2,3-和(6-O-叔丁基二甲基硅基-2,3-二脱氧-D-赤式-己-2-烯吡喃糖基)苯二脱氧-D-赤式-己-2-烯吡喃糖基)苯的环氧化反应，无论异构中心的构型如何，都主要产生异构加合物。(4,6-二-O-叔丁基二甲基硅基-2,3-二脱氧-D-赤式-己-2-烯吡喃糖基)苯的环氧化反应生成了甘露加成物和异伞状加成物，α-异构体和β-异构体的比例分别为 89:11 和 40:60。使用 OsO4 对α-C-苯基-∆2,3-吡喃糖苷进行羟基化反应，无论第 4 和第 6 位的取代基如何，都只能得到甘露加合物，而对（2、3-二脱氧-β-D-赤式-己-2-烯吡喃糖基）苯和（4,6-二-O-叔丁基二甲基硅基-2,3-二脱氧-β-D-赤式-己-2-烯吡喃糖基）苯的羟基化反应得到了甘露加合物和烯丙基加合物，比例分别为 25：75 和 80:20 的比例生成甘露加成物和异羟加成物。

  DOI：

  10.3390/10080859
• 作为产物：
  描述：

  (2R,3S,6R)-6-(4-tert-butylphenoxy)-2-(hydroxymethyl)-3,6-dihydro-2H-pyran-3-ol 在 咪唑 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.0h， 生成 (4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranosyl)benzene
  参考文献：
  名称：

  Synthesis of α- and β-C-Aryl Δ²-Glycopyranosides from p-tert-Butylphenyl Δ²-Glycopyranosides via Grignard Reagents

  摘要：

  Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (1a alpha) or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1b alpha) with various functionalized arylmagnesium bromides in the presence of a catalytic amount of PdCl2(dppf) at 25 degrees C in THF afforded the corresponding unsaturated C-arylglycosides 2-14 having the ct-configuration in quite good yields. Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated alpha-C-glycosides 15-18, although in lower yields. When the same reaction was performed in the presence of NiCl2(dppe) as the catalyst at -40 degrees C, only the formation of the corresponding unsaturated C-arylglycosides having the beta-configuration was observed. As expected, reaction of phenylmagnesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-beta-D-erythro-hex-2-enopyranoside (1a beta) in the presence of NiCl2(dppe) gave only the unsaturated beta-C-phenylglycoside 2a beta, while palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2a alpha. Reaction of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside (20) afforded stereospecifically the unsaturated alpha- and beta-C-phenylglycoside 25 in the presence of PdCl2-(dppf) and NiCl2(dppe), respectively.

  DOI：

  10.1021/jo9714674

文献信息

• Stereochemistry in palladium- and nickel-catalyzed addition of phenylmagnesium bromide to unsaturated carbohydrates
  作者：Christophe Moineau、Véronique Bolitt、Denis Sinou

  DOI：10.1016/s0022-328x(98)00679-2

  日期：1998.9

  Palladium complex PdCl2(dppf) and nickel complex NiCl2(dppe) catalyze cross-coupling of unsaturated aryloxy carbohydrates with phenylmagnesium bromide. The nickel catalyst leads to inversion of configuration at the anomeric center while only retention occurs in the case of the palladium catalyst. This quite unusal retention is probably due to the influence of the ring oxygen atom

  钯配合物PdCl 2（dppf）和镍配合物NiCl 2（dppe）催化不饱和芳氧基碳水化合物与苯基溴化镁的交叉偶联。镍催化剂导致在端基异构体中心的构型反转，而在钯催化剂的情况下仅发生保留。这种非常不常用的保留可能是由于环氧原子的影响
• Titanium tetrachloride mediated reductive ring opening of C-aryl pseudoglycals
  作者：Ch. Raji Reddy、G. Balakrishna Reddy、Ch. Lohitha Rao

  DOI：10.1016/j.tetlet.2007.11.175

  日期：2008.1

  A facile reductive ring opening of C-aryl pseudoglycals is reported for the first time. The combination of titanium tetrachloride (Lewis acid) and triethylsilane (reducing agent) at -78 degrees C in dichloromethane is a mild and efficient reagent system for this transformation. The reagent system was successfully tested on various C-aryl pseudoglycal substrates to yield the corresponding ring opened products containing two asymmetric hydroxyls and a cis-double bond. (C) 2007 Elsevier Ltd. All rights reserved.
• Synthesis of α- and β-<i>C</i>-Aryl Δ²-Glycopyranosides from <i>p</i>-<i>tert</i>-Butylphenyl Δ²-Glycopyranosides via Grignard Reagents
  作者：Christophe Moineau、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo9714674

  日期：1998.2.1

  Treatment of p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (1a alpha) or the 4,6-di-O-(tert-butyldimethylsilyl) analogue (1b alpha) with various functionalized arylmagnesium bromides in the presence of a catalytic amount of PdCl2(dppf) at 25 degrees C in THF afforded the corresponding unsaturated C-arylglycosides 2-14 having the ct-configuration in quite good yields. Benzyl-, allyl-, and vinylmagnesium bromides gave also the corresponding unsaturated alpha-C-glycosides 15-18, although in lower yields. When the same reaction was performed in the presence of NiCl2(dppe) as the catalyst at -40 degrees C, only the formation of the corresponding unsaturated C-arylglycosides having the beta-configuration was observed. As expected, reaction of phenylmagnesium bromide with p-tert-butylphenyl 4,6-di-O-benzyl-2,3-dideoxy-beta-D-erythro-hex-2-enopyranoside (1a beta) in the presence of NiCl2(dppe) gave only the unsaturated beta-C-phenylglycoside 2a beta, while palladium-catalyzed reaction led to the preponderant formation of C-phenylglycoside 2a alpha. Reaction of PhMgBr with p-tert-butylphenyl 4-O-benzyl-2,3,6-trideoxy-alpha-L-erythro-hex-2-enopyranoside (20) afforded stereospecifically the unsaturated alpha- and beta-C-phenylglycoside 25 in the presence of PdCl2-(dppf) and NiCl2(dppe), respectively.
• Epoxidation and Bis-hydroxylation of C-Phenyl-∆2,3-glycopyranosides
  作者：G. Fakha、D. Sinou

  DOI：10.3390/10080859

  日期：——

  Epoxidation and cis-hydroxylation of C-phenyl-∆2,3-glycopyranosides have beencarried out with a view to developing C-aryl glycoside synthesis. Epoxidation of (2,3- and (6-O-tert-butyldimethylsilyl-2,3-dideoxy-D-erythro-hex-2-enopyranosyl)benzenedideoxy-D-erythro-hex-2-enopyranosyl)benzene gave predominantly the allo-adductswhatever the configuration at the anomeric center. Epoxidation of (4,6-di-O-tert-butyl-dimethylsilyl-2,3-dideoxy-D-erythro-hex-2-enopyranosyl)benzene gave the manno- andallo-adducts in a 89:11 and 40:60 ratios for the α- and β-anomers, respectively.Hydroxylation of α-C-phenyl-∆2,3-glycopyranosides using OsO4 afforded the manno-adductonly, whatever the substituents at positions 4 and 6, whereas hydroxylation of (2,3-dideoxy-β-D-erythro-hex-2-enopyranosyl)benzene and (4,6-di-O-tert-butyldimethylsilyl-2,3-dideoxy- β-D-erythro-hex-2-enopyranosyl)benzene gave the manno- and allo-adducts in25:75 and 80:20 ratios, respectively.

  为了发展 C-芳基糖苷的合成，对 C-苯基-Δ2,3-吡喃糖苷进行了环氧化和顺式羟化反应。(2,3-和(6-O-叔丁基二甲基硅基-2,3-二脱氧-D-赤式-己-2-烯吡喃糖基)苯二脱氧-D-赤式-己-2-烯吡喃糖基)苯的环氧化反应，无论异构中心的构型如何，都主要产生异构加合物。(4,6-二-O-叔丁基二甲基硅基-2,3-二脱氧-D-赤式-己-2-烯吡喃糖基)苯的环氧化反应生成了甘露加成物和异伞状加成物，α-异构体和β-异构体的比例分别为 89:11 和 40:60。使用 OsO4 对α-C-苯基-∆2,3-吡喃糖苷进行羟基化反应，无论第 4 和第 6 位的取代基如何，都只能得到甘露加合物，而对（2、3-二脱氧-β-D-赤式-己-2-烯吡喃糖基）苯和（4,6-二-O-叔丁基二甲基硅基-2,3-二脱氧-β-D-赤式-己-2-烯吡喃糖基）苯的羟基化反应得到了甘露加合物和烯丙基加合物，比例分别为 25：75 和 80:20 的比例生成甘露加成物和异羟加成物。