(3R,5R)-hepta-1,6-diene-3,5-diol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R,5R)-hepta-1,6-diene-3,5-diol
• 化学式: C₇H₁₂O₂
• 分子量: 128.171
• InChiKey: PEPISENPCDEXJK-BQBZGAKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,5R)-hepta-1,6-diene-3,5-diol 在 2,6-二甲基吡啶 、 Grubbs catalyst first generation 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 9.0h， 生成 (4R)-(+)-T-丁基二甲基硅氧-1-酮
  参考文献：
  名称：

  Stereodivergent Synthesis of Enantioenriched 4-Hydroxy-2-cyclopentenones

  摘要：

  Protected 4-hydroxycyclopentenones (4-HCPs) constitute an important class of intermediates in chemical synthesis. A route to this class of compound has been developed. Key steps include Noyori reduction (which establishes the stereochemistry of the product), ring-closing metathesis, and simple functional group conversions to provide a set of substituted 4-HCPs in either enantiomeric form.

  DOI：

  10.1021/jo402539p
• 作为产物：
  描述：

  2,4-戊二酮,1,5-二氯 在 正丁基锂 、 [(S)-2,2'-双(二苯基磷)-1,1'-联萘]二氯化钌(II) 、 氢气 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 (3R,5R)-hepta-1,6-diene-3,5-diol
  参考文献：
  名称：

  Stereodivergent Synthesis of Enantioenriched 4-Hydroxy-2-cyclopentenones

  摘要：

  Protected 4-hydroxycyclopentenones (4-HCPs) constitute an important class of intermediates in chemical synthesis. A route to this class of compound has been developed. Key steps include Noyori reduction (which establishes the stereochemistry of the product), ring-closing metathesis, and simple functional group conversions to provide a set of substituted 4-HCPs in either enantiomeric form.

  DOI：

  10.1021/jo402539p

文献信息

• <i>P</i>-Stereogenic Bicyclo[4.3.1]phosphite Boranes: Synthesis and Utility of Tunable <i>P</i>-Tether Systems for the Desymmetrization of <i>C</i>₂-Symmetric 1,3-<i>anti</i>-Diols
  作者：Jana L. Markley、Paul R. Hanson

  DOI：10.1021/acs.orglett.7b00851

  日期：2017.5.19

  1]phosphite borane tether systems for the desymmetrization of C2-symmetric dienediols is reported. This report highlights preliminary studies including tether installation and removal as well as chemoselective functionalization of the exocyclic olefin via diimide reduction or cross-metathesis. Most notably, a divergent oxidation strategy allows for the transformation of the bicyclic phosphite borane complexes

  报道了用于C 2对称二烯二醇去对称化的P-立体异构双环[4.3.1]亚磷酸硼烷系链系统的开发。该报告重点介绍了初步研究，包括系链的安装和去除以及通过二酰亚胺还原或交叉复分解实现的环外烯烃的化学选择性官能化。最值得注意的是，发散的氧化策略允许将双环亚磷酸酯硼烷络合物转化为相应的磷酸盐或硫代磷酸盐系统，从而突出了该P-系链系统的电子衰减。
• Synthesis of the Bryostatin 1 Northern Hemisphere (C1−C16) via Desymmetrization by Ketalization/Ring-Closing Metathesis
  作者：Eric A. Voight、Hassan Seradj、Paul A. Roethle、Steven D. Burke

  DOI：10.1021/ol0483044

  日期：2004.10.1

  [reaction: see text] Synthesis of the northern hemisphere (C1-C16) of bryostatin 1, a potent anticancer agent, has been accomplished in 14 steps and 11% overall yield via desymmetrization by ketalization/ring-closing metathesis. A 2,9-dioxabicyclo[3.3.1]nonane template facilitated stereoselective A-ring functionalization, while an efficient hetero-Diels-Alder reaction was used to elaborate the B-ring

  [反应：见正文]溴代他汀1（一种有效的抗癌剂）在北半球（C1-C16）的合成已通过14个步骤完成，并通过缩酮化/闭环复分解反应实现了11％的总收率。2,9-二氧杂双环[3.3.1]壬烷模板促进了立体选择性A环的功能化，而有效的杂Diels-Alder反应则用于精制B环。
• Stereoselective Total Synthesis of (−)-Kumausallene
  作者：Jenny B. Werness、Weiping Tang

  DOI：10.1021/ol201477u

  日期：2011.7.15

  A stereoselective total synthesis of (-)-kumausallene was completed in 12 steps from acetylacetone. The hidden symmetry of (-)-kumausallene was recognized, and its skeleton was constructed efficiently from a C(2)-symmetric diol by a palladium-catalyzed cascade reaction. High diastereoselectivity was observed for the DMF-promoted biomimetic 1,4-bromocyclization of a conjugated enyne.
• A Novel Route to the F-Ring of Halichondrin B. Diastereoselection in Pd(0)-Mediated <i>meso</i> and <i>C</i>₂ Diol Desymmetrization
  作者：Lei Jiang、Steven D. Burke

  DOI：10.1021/ol026504e

  日期：2002.10.1

  [GRAPHICS]Both sigma and C-2 symmetric diol diacetates were synthesized via two-directional chain elongation. A palladium-mediated, ligand-controlled C-2 diol desymmetrization provided the desired tetrahydrofuran with the correct relative and absolute stereochemistries. Simple functional group manipulation led to the desired F-ring of halichondrin B. Desymmetrization of the meso substrate enantioselectively provided the diastereomer, leading to a refinement of our understanding of the transition state model.
• Total Synthesis of Dolabelide C: A Phosphate-Mediated Approach
  作者：Paul R. Hanson、Rambabu Chegondi、John Nguyen、Christopher D. Thomas、Joshua D. Waetzig、Alan Whitehead

  DOI：10.1021/jo2003506

  日期：2011.6.3

  The first synthesis of dolabelide C (1), a cytotoxic marine macrolide, is reported utilizing a phosphate tether-mediated approach. Bicyclic phosphates (S,S,S-p)-5 and (R,R,R-p)-5 serve as the central building blocks for the construction of two major 1,3-anti-diol subunits in 1 through selective cleavage pathways, regioselective olefin reduction, and cross-metathesis. Overall, phosphate-mediated processes provided copious amounts of both major subunits allowing for a detailed RCM macrocyclization study to the 24-membered macrolactone 1.