(E)-1-(tert-butyldimethylsiloxy)-3-(tributylstannyl)-4,4-dimethyl-pent-1-ene | 345891-87-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (E)-1-(tert-butyldimethylsiloxy)-3-(tributylstannyl)-4,4-dimethyl-pent-1-ene
• 英文别名: tert-butyl-[(E)-4,4-dimethyl-3-tributylstannylpent-1-enoxy]-dimethylsilane
• CAS: 345891-87-4
• 化学式: C₂₅H₅₄OSiSn
• 分子量: 517.499
• InChiKey: RDZVCQMRIIKDHA-ARLMWRGNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.79
• 重原子数：
  28
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (E)-1-(tert-butyldimethylsiloxy)-3-(tributylstannyl)-4,4-dimethyl-pent-1-ene 在 三氟化硼乙醚 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 trans-(E)-3-benzyl-5-(3,3-dimethylbuten-1-yl)-4-phenyloxazolidin-2-one
  参考文献：
  名称：

  Allylstannation of N-acyliminium intermediates: a possible method for the stereocontrolled synthesis of polyhydroxypiperidines

  摘要：

  The stereochemistry of the allylstannation of acyliminium intermediates has been examined for gamma-alkoxyallyltins and gamma-silyloxyallyltributyltins. In the latter case, the reaction has been shown to afford cleanly the syn adduct. Its subsequent ring-closing metathesis and dihydroxylation has allowed the highly stereoselective preparation of a 2-aryl-trihydroxypiperidine. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.11.027
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 (E)-3-(tributylstannyl)acrylaldehyde 、 tBu2Cu(CN)Li2 在 六甲基磷酰三胺 作用下， 以 not given 为溶剂， 生成 (E)-1-(tert-butyldimethylsiloxy)-3-(tributylstannyl)-4,4-dimethyl-pent-1-ene 、 (Z)-1-(tert-butyldimethylsiloxy)-3-(tributylstannyl)-4,4-dimethyl-pent-1-ene
  参考文献：
  名称：

  γ-苄氧基烯丙基烯烃与亚环己基甘油醛的反应活性

  摘要：

  在三氟化硼的存在下，通过烷基氰基戊酸酯与3,3-二苄氧基-1-三丁基锡烷基丙-1-烯的S N 2'反应，以50-80％的产率获得苄氧基烯丙基三丁基锡。他们在不同的路易斯酸存在下与亚环己基甘油醛反应，并通过与真实的醛糖苷酶比较，在臭氧分解/脱保护序列后明确鉴定了所获得的非对映异构体加合物。简要讨论了机理以及试剂构型与烯丙基锡化反应选择性的关系。

  DOI：

  10.1016/s0022-328x(00)00928-1

文献信息

• syn-Allylstannation of N-Acyliminium Intermediates by Tributyl[γ-(silyloxy)allyl]stannanes: A Key Reaction for the Diastereoselective Synthesis of Polyhydroxypiperidines and Polyhydroxyazepanes
  作者：Floris Chevallier、Alexandre Lumbroso、Isabelle Beaudet、Erwan Le Grognec、Loïc Toupet、Jean-Paul Quintard

  DOI：10.1002/ejoc.201100302

  日期：2011.8

  The allylstannation of N-alkenyl N-acyliminium intermediates by tributyl[gamma-(silyloxy)allyl]stannanes afforded the expected adducts with a high syn-selectivity (up to 99: 1). Ensuing ring-closing metathesis afforded dehydropiperidines or dehydroazepanes which were engaged in a stereoselective dihydroxylation reaction leading to polyhydroxypiperidines or polyhydroxyazepanes in good yields. This sequence

  N-烯基N-酰基胺中间体通过三丁基[γ-(甲硅烷氧基)烯丙基]锡烷的烯丙基锡化提供了具有高顺式选择性(高达99:1)的预期加合物。随后的闭环复分解得到脱氢哌啶或脱氢氮杂环庚烷，它们参与立体选择性二羟基化反应，以良好的产率得到多羟基哌啶或聚羟基氮杂环庚烷。该序列被应用于 (+/-)-1-脱氧古洛糖野尻霉素的非对映选择性合成。
• Addition of γ-silyloxyallyltins on ethyl glyoxylate: evaluation of the influence of the experimental conditions on the stereochemical course of the reaction
  作者：Alexandre Lumbroso、Piotr Kwiatkowski、Anna Blonska、Erwan Le Grognec、Isabelle Beaudet、Janusz Jurczak、Slawomir Jarosz、Jean-Paul Quintard

  DOI：10.1016/j.tet.2009.12.037

  日期：2010.2

  Ethyl glyoxylate was reacted with α-substituted γ-(t-butyldimethylsilyloxy)-allyltributyltin in order to obtain selectively each diastereomer of ethyl 3-(t-butyldimethylsilyloxy)-2-hydroxyhex-4-enoate and subsequently the corresponding diols. Diastereomers syn-E, anti-E and anti-Z were obtained in good yields with good to high selectivities and the obtained results were rationalized by consideration

  使乙醛酸乙酯与α-取代的γ-（叔丁基二甲基甲硅烷氧基）-烯丙基三丁基锡反应，以便选择性地获得3-（叔丁基二甲基甲硅烷氧基）-2-羟基己基-4-烯酸酯的每个非对映异构体，然后得到相应的二醇。非对映体顺式- ë，抗- Ë和抗- ž与良好的高选择性和获得的结果良好的收益率在协议被考虑，环状或开过渡态的合理化与实验条件和起始试剂的结构中获得。
• Reactivity of γ-benzyloxyallyltins with cyclohexylidene glyceraldehydes
  作者：Florian Fliegel、Isabelle Beaudet、Jean-Paul Quintard

  DOI：10.1016/s0022-328x(00)00928-1

  日期：2001.4

  yield by SN2′ reaction of alkyl-cyanocuprates with 3,3-dibenzyloxy-1-tributylstannylprop-1-ene in the presence of boron trifluoride. They reacted with cyclohexylidene glyceraldehyde in the presence of different Lewis acids and the obtained diastereomeric adducts were unambiguously identified after an ozonolysis/deprotection sequence by comparison with authentic aldopentoses. The mechanisms are briefly

  在三氟化硼的存在下，通过烷基氰基戊酸酯与3,3-二苄氧基-1-三丁基锡烷基丙-1-烯的S N 2'反应，以50-80％的产率获得苄氧基烯丙基三丁基锡。他们在不同的路易斯酸存在下与亚环己基甘油醛反应，并通过与真实的醛糖苷酶比较，在臭氧分解/脱保护序列后明确鉴定了所获得的非对映异构体加合物。简要讨论了机理以及试剂构型与烯丙基锡化反应选择性的关系。
• Allylstannation of N-acyliminium intermediates: a possible method for the stereocontrolled synthesis of polyhydroxypiperidines
  作者：Floris Chevallier、Isabelle Beaudet、Erwan Le Grognec、Loı̈c Toupet、Jean-Paul Quintard

  DOI：10.1016/j.tetlet.2003.11.027

  日期：2004.1

  The stereochemistry of the allylstannation of acyliminium intermediates has been examined for gamma-alkoxyallyltins and gamma-silyloxyallyltributyltins. In the latter case, the reaction has been shown to afford cleanly the syn adduct. Its subsequent ring-closing metathesis and dihydroxylation has allowed the highly stereoselective preparation of a 2-aryl-trihydroxypiperidine. (C) 2003 Elsevier Ltd. All rights reserved.