(2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane | 159292-96-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane
• 英文别名: (2S,3S)-tert-butyl-(2-iodomethyl-tetrahydro-pyran-3-yloxy)-dimethyl-silane；(2S,3S)-3-(tert-Butyldimethylsiloxy)-3,4,5,6-tetrahydro-2H-pyran-2-iodomethane；1,2,3,6-tetradeoxy-6-iodo-4-O-tert-butyldimethylsilyl-D-glucopyranose；tert-butyl-[(2S,3S)-2-(iodomethyl)oxan-3-yl]oxy-dimethylsilane
• CAS: 159292-96-3
• 化学式: C₁₂H₂₅IO₂Si
• 分子量: 356.319
• InChiKey: JAKCXAGHVLYLFN-WDEREUQCSA-N

物化性质

• 沸点：
  318.4±27.0 °C(predicted)
• 密度：
  1.28±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane 在 四氧化锇 sodium periodate 、 偶氮二异丁腈 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 水 、 sodium hydride 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 苯 为溶剂， 反应 19.75h， 生成 (4aS,6S,7S,9aR)-7-(tert-Butyl-dimethyl-silanyloxy)-octahydro-1,5-dioxa-benzocycloheptene-6-carbaldehyde
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034
• 作为产物：
  描述：

  1,5-Anhydro-4,6-bis(tert-butyldimethylsilyl)-2,3-dideoxy-D-erythro-hexitol 在 咪唑 、 碘 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 水 、 苯 为溶剂， 反应 3.58h， 生成 (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034

文献信息

• Convergent Synthesis of the E‘FGH‘ Ring Fragment of Ciguatoxin 1B via an Acetylene Cobalt Complex Strategy
  作者：Shigeyuki Takai、Minoru Isobe

  DOI：10.1021/ol0256264

  日期：2002.4.1

  [reaction: see text] A convergent synthesis of the E'FGH' ring fragment of ciguatoxin has been accomplished through (i) coupling between the E' ring-acetylide and the H' ring-aldehyde, (ii) stereoselective F ring cyclization via an acetylene cobalt complex, (iii) conversion to a carbonyl function, and (iv) reductive hydroxy-ketone cyclization to construct the G ring.

  [反应：见正文]通过（i）E'环乙炔化物和H'环醛之间的偶联，（ii）通过以下方式的立体选择性F环环化，实现了瓜瓜毒素E'FGH'环片段的聚合合成乙炔钴配合物，（iii）转化为羰基官能团，和（iv）还原性羟基-酮环化以构建G环。
• An efficient strategy for the iterative synthesis of a trans-fused polytetrahydropyran ring system via SmI2-induced reductive intramolecular cyclization
  作者：Nobuyuki Hori、Hiroko Matsukura、Goh Matsuo、Tadashi Nakata

  DOI：10.1016/s0040-4039(99)00301-9

  日期：1999.4

  A highly efficient strategy for the iterative synthesis of a trans-fused polytetrahydropyran ring system was developed. The new iterative method involves SmI2-induced reductive intramolecular cyclization of an aldehyde and a β-alkoxy acrylate as the key step, producing a 2,3-trans-tetrahydropyran ring.

  开发了一种高效的策略，用于迭代合成反式聚四氢吡喃环系统。新的迭代方法涉及作为关键步骤的SmI 2诱导的醛和β-烷氧基丙烯酸酯的还原性分子内环化，生成2，3-反式-四氢吡喃环。
• Efficient strategy for the iterative synthesis of trans-fused polycyclic ether via SmI2-induced reductive intramolecular cyclization
  作者：Nobuyuki Hori、Hiroko Matsukura、Goh Matsuo、Tadashi Nakata

  DOI：10.1016/s0040-4020(02)00042-x

  日期：2002.3

  A highly efficient strategy for the iterative synthesis of a trans-fused polycyclic ether ring system has been developed. The new iterative method involves SmI2-induced reductive intramolecular cyclization of an aldehyde and a β-alkoxy acrylate as the key step, producing a 2,3-trans-tetrahydropyran or oxepane ring. The syntheses of trans-fused 6,6,6-tricyclic, 6,7,6-tricyclic, and 6,7,7,6-tetracyclic

  已经开发出用于反式稠合多环醚环系统的迭代合成的高效策略。新的迭代方法涉及作为关键步骤的SmI 2诱导的醛和β-烷氧基丙烯酸酯的还原性分子内环化，生成2，3-反式-四氢吡喃或氧杂环丁烷环。基于新开发的方法，可以有效地实现反式稠合的6,6,6-三环醚，6,7,6-三环醚和6,7,7,6-四环醚的合成。
• Stereoselective syntheses of trans-fused 6,6- and 6,7-membered ether ring systems having an angular methyl group based on SmI2-induced reductive intramolecular cyclization
  作者：Goh Matsuo、Nobuyuki Hori、Tadashi Nakata

  DOI：10.1016/s0040-4039(99)01861-4

  日期：1999.12

  Highly stereoselective syntheses of trans-fused 6,6- and 6,7-membered ether ring systems having an angular methyl group were achieved based on SmI2-induced reductive intramolecular cyclizations of an aldehyde or a methyl ketone and a β-alkoxy acrylate.

  基于SmI 2诱导的醛或甲基酮和β-烷氧基丙烯酸酯的还原性分子内环化反应，实现了具有角甲基的反式稠合的6,6-和6,7-元醚环系统的高度立体选择性合成。
• Ring-Closing Metathesis in the Synthesis of Large and Medium-Sized Oxacycles. Application to the Synthesis of Polyoxygenated Macrocycles
  作者：Mercedes Delgado、Julio D. Martín

  DOI：10.1021/jo9901438

  日期：1999.6.1

  Ring-closing olefin metathesis (RCM) catalyzed by Grubbs's ruthenium benzylidene complex 1 is applied to the synthesis of unsaturated rings ranging in size from seven to thirteen members in trans-fused polyether systems. Reaction occurs with great efficiency in the cyclization of oxepene and oxocene rings, but as ring size increases, yields drop. The influence of the final double bond position is also studied. Better yields and milder reaction conditions are observed when an additional oxygen atom is introduced on the diene. This feature has promoted the application of this reaction to the synthesis of polyoxygenated macrocycles (with sizes ranging from 15 to 21 members), with excellent results.