(Z)-1-benzyloxy-3-tributylstannylbut-1-ene | 345891-85-2

• 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: (Z)-1-benzyloxy-3-tributylstannylbut-1-ene
• 英文别名: α-methyl-γ-benzoyloxyallyltributyltin；tributyl-[(Z)-4-phenylmethoxybut-3-en-2-yl]stannane
• CAS: 345891-85-2
• 化学式: C₂₃H₄₀OSn
• 分子量: 451.28
• InChiKey: RQALRZSGIJLUIR-ZCOCVFMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.96
• 重原子数：
  25
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  (Z)-1-benzyloxy-3-tributylstannylbut-1-ene 、 ethyl N-allyl-N-(ethoxyphenylmethyl)carbamate 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 生成 (E)-ethyl N-allyl-N-[2-benzyloxy-1-phenylpent-3-enyl]carbamate
  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：

  3,3-dibenzoyloxy-1-tributylstannylprop-1-ene 、 甲基氯化镁 在 三氟化硼乙醚 、 copper(l) cyanide 作用下， 以 乙醚 为溶剂， 以51%的产率得到(Z)-1-benzyloxy-3-tributylstannylbut-1-ene
  参考文献：
  名称：

  Preparation of α-substituted γ-alkoxyallylstannanes from β-tributylstannyl acrolein acetals: scope of the method and primary rationalization of the obtained results

  摘要：

  alpha-Substituted gamma-alkoxyallylstannanes were obtained from beta-tributylstannyl acrolein acetals when reacted with lower order magnesium cyanocuprates in the presence of boron trifluoride at low temperature. In the case of n-alkylcyanocuprates an anti S(N)2' substitution on a cisoid conformation appears to be the main reaction pathway. However, subtle competitions with other mechanisms may occur depending on the experimental conditions, on the reagents or on the substrates. These drawbacks constitute limitations for the use of the method especially when enantioenriched alpha-substituted gamma-alkoxyallylstannanes are desired. (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2004.10.022

文献信息

• 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。
• 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。