(+)-(2S,3R,4R)-2,4-bis(tert-butyldimethylsiloxy)-3,5-dimethylhexan-1-ol | 381247-09-2

• 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: (+)-(2S,3R,4R)-2,4-bis(tert-butyldimethylsiloxy)-3,5-dimethylhexan-1-ol
• 英文别名: (2S,3R,4R)-2,4-bis(tert-butyldimethylsilyloxy)-3,5-dimethylhexan-1-ol；(2S,3R,4R)-2,4-bis[[tert-butyl(dimethyl)silyl]oxy]-3,5-dimethylhexan-1-ol
• CAS: 381247-09-2
• 化学式: C₂₀H₄₆O₃Si₂
• 分子量: 390.754
• InChiKey: PIGBVFKDLPUUGA-RCCFBDPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.05
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(2S,3R,4R)-2,4-bis(tert-butyldimethylsiloxy)-3,5-dimethylhexan-1-ol 在 咪唑 、 六甲基磷酰三胺 、 pyridine-SO3 complex 、 四丁基氟化铵 、 碘 、 叔丁基锂 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 、 正戊烷 为溶剂， 反应 16.5h， 生成 (1R)-1-[(4R,5S,6R)-6-((S)-1-{2-[(2R,3S,4R)-2,4-bis(tert-butyldimethylsilanyloxy)-3,5-dimethylhexyl]-[1,3]dithian-2-yl}-ethyl)-2,2,5-trimethyl-[1,3]dioxan-4-yl]-prop-2-yn-1-ol
  参考文献：
  名称：

  Total Synthesis of Bafilomycin A₁ Relying on Iterative 1,2-Induction in Acyclic Precursors

  摘要：

  The macrolide bafilomycin A(1) was synthesized starting from D-valine and D-mannitol as chiral progenitors of propionate units. Acyclic subunits corresponding to different parts of the molecule were constructed based on an iterative 1,2-asymmetric induction protocol as a distinctive feature of the synthesis. The assembly of two segments encompassing the entire carbon framework of the macrolide was achieved by using a Stille coupling. The resulting seco-ester was further manipulated to provide crystalline bafilomycin A(1) via a conventional carbodiimide-mediated Keck-type macrolactonization.

  DOI：

  10.1021/ja011452u
• 作为产物：
  描述：

  D-缬氨酸 在 palladium dihydroxide 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 三甲基氯硅烷 、 草酰氯 、 硫酸 、 氢气 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 二甲基亚砜 、 N,N-二异丙基乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， -78.0~130.0 ℃ 、101.33 kPa 条件下， 反应 98.0h， 生成 (+)-(2S,3R,4R)-2,4-bis(tert-butyldimethylsiloxy)-3,5-dimethylhexan-1-ol
  参考文献：
  名称：

  Total Synthesis of Bafilomycin A₁ Relying on Iterative 1,2-Induction in Acyclic Precursors

  摘要：

  The macrolide bafilomycin A(1) was synthesized starting from D-valine and D-mannitol as chiral progenitors of propionate units. Acyclic subunits corresponding to different parts of the molecule were constructed based on an iterative 1,2-asymmetric induction protocol as a distinctive feature of the synthesis. The assembly of two segments encompassing the entire carbon framework of the macrolide was achieved by using a Stille coupling. The resulting seco-ester was further manipulated to provide crystalline bafilomycin A(1) via a conventional carbodiimide-mediated Keck-type macrolactonization.

  DOI：

  10.1021/ja011452u

文献信息

• Concise epoxide-based synthesis of the C14–C25 bafilomycin A1 polypropionate chain
  作者：Elizabeth M. Valentín、Marlenne Mulero、José A. Prieto

  DOI：10.1016/j.tetlet.2012.02.067

  日期：2012.4

  An efficient nonaldol convergent synthesis of the C14–C25 polyketide fragment of bafilomycin A1 was completed in 16% overall yield and 8 steps in its longest linear sequence. This synthesis highlights the formation of the key fragments using a three-step sequence of epoxide cleavage, alkyne reduction, and epoxidation developed in our laboratory; starting from suitably protected enantiomeric epoxides

  bafilomycin A 1的 C14-C25 聚酮化合物片段的高效壬醛聚合合成以 16% 的总产率和最长线性序列的 8 个步骤完成。该合成使用我们实验室开发的环氧化物裂解、炔烃还原和环氧化的三步序列突出了关键片段的形成；从适当保护的反式-2,3-环氧丁醇的对映体环氧化物开始。这种化学反应代表了巴弗洛霉素 A 1聚酮链的快速不对称和非对映选择性构建，其中每个立体中心都是仅使用环氧化物化学构建的。
• Synthesis of the C14−C25 Subunit of Bafilomycin A₁
  作者：Florence Eustache、Peter I. Dalko、Janine Cossy

  DOI：10.1021/jo035068m

  日期：2003.12.1

  sequence involves two dynamic kinetic resolution steps of 2-alkyl 1,3-diketones that use optically active ruthenium complexes, an anti-selective reduction of a beta-hydroxyketone to control the C23 stereogenic center, and an aldol-type reaction under Evans' conditions, which sets the C17 and C18 stereogenic centers.

  通过收敛的途径实现了对bafilomycin A1的C14-C25亚基的对映选择性合成。该序列涉及两个动态动力学拆分步骤，即使用光学活性钌配合物的2-烷基1,3-二酮，反选择性还原β-羟基酮以控制C23立体异构中心以及在Evans's反应下的醛醇型反应。条件，这将设置C17和C18立体定位中心。
• Enantioselective monoreduction of 2-alkyl 1,3-diketones using chiral ruthenium catalysts. Synthesis of the C14C25 fragment of bafilomycin A1
  作者：Florence Eustache、Peter I. Dalko、Janine Cossy

  DOI：10.1016/j.tetlet.2003.09.192

  日期：2003.12

  The enantioselective monoreduction of 2-alkyl 1,3-diketones by dynamic kinetic resolution using optically active ruthenium catalysts allowed the preparation of the C14–C25 fragment of bafilomycin A1.

  通过使用旋光性钌催化剂的动态动力学拆分，对2-烷基1,3-二酮进行对映选择性单还原，从而制备了巴氟霉素A 1的C14–C25片段。
• Total Synthesis of Bafilomycin A₁ Relying on Iterative 1,2-Induction in Acyclic Precursors
  作者：Stephen Hanessian、Jianguo Ma、Wengui Wang

  DOI：10.1021/ja011452u

  日期：2001.10.1

  The macrolide bafilomycin A(1) was synthesized starting from D-valine and D-mannitol as chiral progenitors of propionate units. Acyclic subunits corresponding to different parts of the molecule were constructed based on an iterative 1,2-asymmetric induction protocol as a distinctive feature of the synthesis. The assembly of two segments encompassing the entire carbon framework of the macrolide was achieved by using a Stille coupling. The resulting seco-ester was further manipulated to provide crystalline bafilomycin A(1) via a conventional carbodiimide-mediated Keck-type macrolactonization.