methyl 2-[(1S,2S,6R,7S,9S,12R)-7-[(E,1S)-1-hydroxy-3-trimethylsilylprop-2-enyl]spiro[3,5,8,13-tetraoxatricyclo[7.4.0.02,6]tridecane-4,1'-cyclohexane]-12-yl]acetate | 185411-10-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: methyl 2-[(1S,2S,6R,7S,9S,12R)-7-[(E,1S)-1-hydroxy-3-trimethylsilylprop-2-enyl]spiro[3,5,8,13-tetraoxatricyclo[7.4.0.02,6]tridecane-4,1'-cyclohexane]-12-yl]acetate
• CAS: 185411-10-3
• 化学式: C₂₃H₃₈O₇Si
• 分子量: 454.636
• InChiKey: BSHVAIKUWAPZSA-SYCWTHGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  83.4
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2-[(1S,2S,6R,7S,9S,12R)-7-[(E,1S)-1-hydroxy-3-trimethylsilylprop-2-enyl]spiro[3,5,8,13-tetraoxatricyclo[7.4.0.02,6]tridecane-4,1'-cyclohexane]-12-yl]acetate 在 溶剂黄146 作用下， 以 水 、 三氟乙酸 为溶剂， 生成 艾日布林中间体,艾瑞布林中间体
  参考文献：
  名称：

  Synthetic studies on halichondrins: A practical synthesis of the C.1C.13 segment

  摘要：

  A practical, scalable synthesis of the C.1-C.13 segment of halichondrin B has been developed starting from L-mannonic-gamma-lactone, using C-allylation/oxy-Michael cyclization and Ni(II)/Cr(II)-mediated vinyltrimethylsilane addition to set the C.6/C.3 and C.11 stereocenters, respectively. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)01999-5
• 作为产物：
  描述：

  三丁基[(1E)-2-(三甲基硅烷基)乙烯基]锡烷 在 chromium dichloride 、 碘 、 nickel dichloride 作用下， 以 二氯甲烷 、 二甲基亚砜 为溶剂， 生成 methyl 2-[(1S,2S,6R,7S,9S,12R)-7-[(E,1S)-1-hydroxy-3-trimethylsilylprop-2-enyl]spiro[3,5,8,13-tetraoxatricyclo[7.4.0.02,6]tridecane-4,1'-cyclohexane]-12-yl]acetate
  参考文献：
  名称：

  Synthetic studies on halichondrins: A practical synthesis of the C.1C.13 segment

  摘要：

  A practical, scalable synthesis of the C.1-C.13 segment of halichondrin B has been developed starting from L-mannonic-gamma-lactone, using C-allylation/oxy-Michael cyclization and Ni(II)/Cr(II)-mediated vinyltrimethylsilane addition to set the C.6/C.3 and C.11 stereocenters, respectively. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4039(96)01999-5

文献信息

• Ni(II)/Cr(II)-Mediated Coupling Reaction: Beneficial Effects of 4-tert-Butylpyridine as an Additive and Development of New and Improved Workup Procedures
  作者：Dean P Stamos、X.Christopher Sheng、Sean S Chen、Yoshito Kishi

  DOI：10.1016/s0040-4039(97)01462-7

  日期：1997.9

  4-tert-Butylpyridine has been shown to be a beneficial additive in the Ni(II)/Cr(II)-mediated coupling reaction. This additive allows for homogeneous reactions, improves reproducibility, and inhibits homo-coupling of vinyl iodides or triflates. Improved workup procedures using chromium ion chelators (ethylenediamine or sodium or potassium serinate) allow for a better mass recovery. © 1997 Elsevier

  已经证明4-叔丁基吡啶是Ni（II）/ Cr（II）介导的偶联反应中的有益添加剂。该添加剂可进行均相反应，提高重现性，并抑制乙烯基碘或三氟甲磺酸酯的均相偶联。使用铬离子螯合剂（乙二胺或丝氨酸钠或丝氨酸钾）的改进后处理程序可实现更好的质量回收率。©1997爱思唯尔科学有限公司。
• Toolbox Approach to the Search for Effective Ligands for Catalytic Asymmetric Cr-Mediated Coupling Reactions
  作者：Haibing Guo、Cheng-Guo Dong、Dae-Shik Kim、Daisuke Urabe、Jiashi Wang、Joseph T. Kim、Xiang Liu、Takeo Sasaki、Yoshito Kishi

  DOI：10.1021/ja905843e

  日期：2009.10.28

  Chromium catalysts derived from chiral sulfonamides represented by A effect the couplings of aldehydes with vinyl, allyl, or alkyl halides. With three distinct sites for structural modification, A affords access to a structurally diverse pool of chiral sulfonamides. The Cr catalysts derived from these sulfonamides exhibit a broad range of catalyst-substrate matching profiles. A strategy is presented to search for a satisfactory chiral sulfonamide for a given substrate. In order to demonstrate the generality and effectiveness of this approach, five diverse C-C bond-forming cases have been selected from the halichondrin synthesis. For each of the cases, two ligands have been deliberately searched for, to induce the formation of (R)and (S)-alcohols, respectively, at the arbitrarily chosen efficiency level of ">= 80% yield with >= 20:1 stereoselectivity in the presence of <= 20 mol % of a Cr catalyst". For 9 out of the 10 cases studied, a satisfactory catalyst has been found within this pool of sulfonamides. Even for the remaining case, a Cr catalyst inducing stereoselectivity up to 8:1 has been identified.