(E)-(4S,5S)-6-<(tert-Butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenal | 151265-91-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-(4S,5S)-6-<(tert-Butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenal
• 英文别名: (2E,4S,5S)-6-[(tert-butyldimethylsilyl)oxy]-4,5-(isopropylidenedioxy)hex-2-enal；(E)-3-[(4S,5S)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]prop-2-enal
• CAS: 151265-91-7
• 化学式: C₁₅H₂₈O₄Si
• 分子量: 300.47
• InChiKey: HZRSUYZUTCXIDL-TYDXBBDOSA-N

物化性质

• 沸点：
  366.8±37.0 °C(predicted)
• 密度：
  0.986±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.28
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-(4S,5S)-6-<(tert-Butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenal 在 platinum on activated charcoal 、 Grubbs catalyst first generation 盐酸 、 四溴化碳 、 四丁基氟化铵 、 氢气 、 phosphorus pentoxide 、 potassium carbonate 、 caesium carbonate 、 Α,Α-二苯基-N-甲基-L-脯氨醇 、 溶剂黄146 、 苯硫酚 、 三乙胺 、 三苯基膦 、 锌 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 环己烷 、 乙腈 、 苯 为溶剂， 反应 6.0h， 生成 (+)-lentiginosine
  参考文献：
  名称：

  Stereoselective Allyl AmineSynthesis via Enantioselective Addition ofDiethylzincand Sigmatropic Rearrangement; Synthesis of Lentiginosine

  摘要：

  一种制备烯丙胺衍生物的新合成方法已经开发出来。该方法的关键步骤是二乙基锌的对映选择性加成（Soai协议）和烯丙氰酸酯到异氰酸酯的重排。该方法的成功应用实现了亮氨酸（6）的合成。

  DOI：

  10.1055/s-2003-39314
• 作为产物：
  描述：

  6-<(tert-butyldimethylsilyl)oxy>-4(S),5(S)-(isopropylidenedioxy)-2(E)-hexen-1-ol 在 2-碘酰基苯甲酸 作用下， 以 二甲基亚砜 为溶剂， 以90%的产率得到(E)-(4S,5S)-6-<(tert-Butyldimethylsilyl)oxy>-4,5-O-(1-methylethylidene)-2-hexenal
  参考文献：
  名称：

  Stereoselective Allyl AmineSynthesis via Enantioselective Addition ofDiethylzincand Sigmatropic Rearrangement; Synthesis of Lentiginosine

  摘要：

  一种制备烯丙胺衍生物的新合成方法已经开发出来。该方法的关键步骤是二乙基锌的对映选择性加成（Soai协议）和烯丙氰酸酯到异氰酸酯的重排。该方法的成功应用实现了亮氨酸（6）的合成。

  DOI：

  10.1055/s-2003-39314

文献信息

• Stereoselective Synthesis of Higher Sugars by Homologation of Carbohydrate-Derived Enals with Nonracemic .gamma.-(Silyloxy) Allylic Stannanes and Substrate-Directed Hydroxylation
  作者：James A. Marshall、Serge Beaudoin

  DOI：10.1021/jo00101a020

  日期：1994.11

  A strategy is described for the chain extension of carbohydrate derivatives utilizing sequential Horner-Emmons condensation and then reduction-oxidation to prepare the enal homologue VII, which is converted to the corresponding dienyl bis-OTBS derivative IX upon condensation with a gamma-(silyloxy) allylic stannane VI and subsequent silylation. Dihydroxylation of dienes M with OsO4-NMO leads to syn,anti,syn,anti,syn. hexol derivatives X with excellent diastereoselectivity. These hexols undergo selective oxidative cleavage with H5IO6 to yield gamma-lactols XI. The methodology has been used to prepare the octonic lactone 15 from (S,S)-dimethyl tartrate and the undeconic lactone 32 from D-mannitol.
• Stereoselective synthesis of long-chain polyols by sequential homologation of enals with nonracemic .gamma.-silyloxy allylic stannanes and directed hydroxylation
  作者：James A. Marshall、Serge Beaudoin、Krzysztof Lewinski

  DOI：10.1021/jo00074a004

  日期：1993.10

  The nonracemic gamma-silyloxy allylic stannanes (S)-8 and (R)-8 add to the (R,R)-tartrate derived enals 7 and 24 to afford the adducts 9, 14, and 25. The bis-TBS derivatives 10, 15 and 22, upon hydroxylation with catalytic 0804-NMO, yield the differentially protected polyols 11, 16, and 23.
• Stereoselective Allyl Amine Synthesis through Enantioselective Addition of Diethylzinc and [1,3]-Chirality Transfer: Synthesis of Lentiginosine and Polyoxamic Acid Derivative
  作者：Yoshiyasu Ichikawa、Takashi Ito、Minoru Isobe

  DOI：10.1002/chem.200400830

  日期：2005.3.4

  synthetic method for the preparation of allyl amines has been developed. The key steps of this method are enantioselective addition of diethylzinc and [1,3]-chirality transfer through the [3.3] sigmatropic rearrangement of allyl cyanates. Stereocontrolled syntheses of lentiginosine (1) and polyoxamic acid derivative 2 from a common intermediate 7 derived from D-tartaric acid (8), have been accomplished.

  已经开发出一种新的制备烯丙基胺的合成方法。该方法的关键步骤是二乙基锌的对映选择性加成和通过[3.3]烯丙基氰酸酯的σ重排而进行的[1,3]-手性转移。已从衍生自D-酒石酸（8）的常见中间体7进行了立体控制的龙胆草碱（1）和聚草酰胺酸衍生物2的立体合成。
• Stereoselective Allyl AmineSynthesis via Enantioselective Addition ofDiethylzincand Sigmatropic Rearrangement; Synthesis of Lentiginosine
  作者：Yoshiyasu Ichikawa、Takashi Ito、Taihei Nishiyama、Minoru Isobe

  DOI：10.1055/s-2003-39314

  日期：——

  A new synthetic method for the preparation of allyl amine derivatives has been developed. The key steps of this method are enantioselective addition of diethylzinc (Soai protocol) and allyl cyanate-to-isocyanate rearrangement. Successful application of this procedure realized the synthesis of lentiginosine (6).

  一种制备烯丙胺衍生物的新合成方法已经开发出来。该方法的关键步骤是二乙基锌的对映选择性加成（Soai协议）和烯丙氰酸酯到异氰酸酯的重排。该方法的成功应用实现了亮氨酸（6）的合成。