p-tert-butylphenyl 4,6-di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside | 201232-73-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: p-tert-butylphenyl 4,6-di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
• 英文别名: p-tert-butylphenyl 4,6-di-O-tert-butyl(dimethyl)silyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside；tert-butyl-[[(2R,3S,6R)-3-[tert-butyl(dimethyl)silyl]oxy-6-(4-tert-butylphenoxy)-3,6-dihydro-2H-pyran-2-yl]methoxy]-dimethylsilane
• CAS: 201232-73-7
• 化学式: C₂₈H₅₀O₄Si₂
• 分子量: 506.874
• InChiKey: SXKRQGQYXMGNKK-GVAUOCQISA-N

物化性质

• 沸点：
  497.9±45.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.06
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  p-tert-butylphenyl 4,6-di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 [Rh(COD)(1,4-bis(diphenylphosphino)butane)]ClO₄ 四丁基氟化铵 、 氢气 、 magnesium 作用下， 以 四氢呋喃 、 乙醇 、 甲苯 为溶剂， 20.0~45.0 ℃ 、101.33 kPa 条件下， 反应 53.0h， 生成 (1S,6R,8R)-3-(4''-butyloxyphenyl)-8-(4'-chlorophenyl)-2,4,7-trioxa-3-borabicyclo[4.4.0]decane
  参考文献：
  名称：

  苯基环上带有卤素取代基的新型三氧十氢萘衍生液晶的立体有择合成

  摘要：

  假葡糖醛 2 与各种带有卤素取代基的芳基格氏试剂在催化量的 NiCl2(dppe) 存在下反应得到相应的 β-C-芳基糖苷 4。4 的脱乙酰和氢化产生 β-C-芳基苷5，可作为手性化合物用于手性液晶的合成。化合物5与脂肪醛反应生成化合物6；类似地，与对烷氧基取代的苯基硼酸反应得到硼酸类似物 7。所有介晶性质强烈依赖于分子结构的微小变化。可以获得多种不同的手性效应，例如螺旋反转、蓝相、TGA 相、胆甾相和近晶 A 相，仅举几例，

  DOI：

  10.1002/1099-0690(200101)2001:2<375::aid-ejoc375>3.0.co;2-j
• 作为产物：
  描述：

  4-t-butylphenyl4, 6-di-O-acetyl-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 咪唑 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 49.0h， 生成 p-tert-butylphenyl 4,6-di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  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
• Bertini, Bruno; Sinou, Denis; Vill, Volkmar, Journal of Chemical Research, Miniprint, 2001, # 11, p. 1144 - 1171
  作者：Bertini, Bruno、Sinou, Denis、Vill, Volkmar

  DOI：——

  日期：——
• ENANTIOPURE TRIOXADECALIN DERIVED LIQUID CRYSTALS: INFLUENCE OF PHENYL SUBSTITUTION ON THE MESOGENIC PROPERTIES
  作者：Bruno Bertini、Christophe Moineau、Denis Sinou、Volkmar Vill

  DOI：10.1081/car-100104867

  日期：2001.4.30

  Nickel(0)-catalyzed reaction of pseudo-glucal 1 with Grignard reagents derived from bromobenzene and 1-bromo-4-phenylbenzene gives the corresponding beta -C-aryl glycosides 2. Desilylation and hydrogenation of 2 leads to saturated beta -C-aryl glycosides 4, which can be used as chiral intermediates in the synthesis of chiral liquid crystals. The combination with p-alkoxy-substituted benzaldehyde leads to compounds 5-6. Alternatively, reaction with p-alkoxy-substituted phenylboronic acids gives the bora analogues 7-9. The mesogenic properties of these compounds are strongly influenced by the presence of an additional phenyl ring in the molecule.
• Enantiopure Trioxadecalin Derived Liquid Crystals: Influence of the Nature of the Phenyl Substituent on the Mesogenic Properties
  作者：Bruno Bertini、Monique Perrin、Denis Sinou、Alain Thozet、Volkmar Vill

  DOI：10.1081/car-120026468

  日期：2003.12.31

  Reaction of pseudo-glucal 1 with Grignard reagents derived from 1-bromo-4(trimethylsilyloxy)benzene, 1-bromo-4-methoxybenzene, 1-bromo-4-methoxymethoxybenzene, 1-bromo-4-dimethylaminobenzene, in the presence of a catalytic amount of NiCl2(dppe), gives the corresponding unsaturated beta-C-aryl glycosides 2. Desilylation and hydrogenation of 2 leads to beta-C-aryl glycosides 4, which can be used as chiral precursor compounds in the synthesis of chiral liquid crystals. Combination of 4 with arylaldehydes leads to compounds 5-7, whereas reaction with p-alkoxysubstituted phenylboronic acids gives the trioxaboradecalins 8-11. The mesogenic properties of these compounds are strongly influenced by the nature of the substituent on the phenyl ring in the molecule.
• Stereoselective synthesis of C-glycosyl analogues of phenylalanine
  作者：Xin Xu、Ghada Fakha、Denis Sinou

  DOI：10.1016/s0040-4020(02)00831-1

  日期：2002.9

  Condensation of]-[4,6-di-O-(tert-butyldimethylsilyl)-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranosyl]-4-bromobenzene (2) with methyl 2-acetamidoacrylate in the presence of Pd(OAc)(2), P(C6H4-O-CH3)(3), and AgNO3, afforded the unsaturated C-glycosyl enamido ester 3d in 80% yield. Reduction of compound 3d in the presence of [Rh(COD)(R,R)-(Et-DuPHOS)]OTf gave the corresponding unsaturated C-glycosyl (R)-phenylalanine derivative, when the [Rh(COD)(S,S)-(Et-DuPHOS)]OTf catalyst gave the C-glycosyl (S)-phenylalanine derivative, in 67 and 79% yield, respectively. Bis-hydroxylation of compound 4, followed by acetylation afforded the C-mannopyranosyl phenylalanine derivative 5 in overall 30% yield. (C) 2002 Elsevier Science Ltd. All rights reserved.