tert-butyl-[(2R,3S,4R)-3-[(4-methoxyphenyl)methoxy]-2,4-dimethylhex-5-enoxy]-dimethylsilane | 1003890-33-2

• 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: tert-butyl-[(2R,3S,4R)-3-[(4-methoxyphenyl)methoxy]-2,4-dimethylhex-5-enoxy]-dimethylsilane
• CAS: 1003890-33-2
• 化学式: C₂₂H₃₈O₃Si
• 分子量: 378.627
• InChiKey: ABKDBVZIVJWNFG-OPYAIIAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.06
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,6R,8R)-8-Vinyl-2,9,10-trioxa-1-phospha-bicyclo[4.3.1]dec-4-ene 1-oxide 、 tert-butyl-[(2R,3S,4R)-3-[(4-methoxyphenyl)methoxy]-2,4-dimethylhex-5-enoxy]-dimethylsilane 在 Hoveyda-Grubbs catalyst second generation 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.5h， 以72%的产率得到(1R,6R,8R)-8-((3R,4S,5R,E)-6-((tert-butyldimethylsilyl)oxy)-4-((4-methoxybenzyl)oxy)-3,5-dimethylhex-1-en-1-yl)-2,9,10-trioxa-1-phosphabicyclo[4.3.1]dec-4-ene 1-oxide
  参考文献：
  名称：

  A Multifaceted Phosphate Tether:  Application to the C1−C14 Subunit of Dolabelides A−D

  摘要：

  A phosphate tether approach to the C1-14 subunit of dolabelide is described. The phosphate tether serves a multifaceted role mediating several processes, including (i) diastereotopic differentiation via RCM, (ii) selective CM by imparting Type III behavior to the exocyclic olefin, (iii) regioselective hydrogenation, and (iv) regioselective Pd(0)-catalyzed reductive opening of the bicyclic phosphate. Overall, this strategy uses orthogonal protecting- and leaving-group properties innate to phosphate esters to rapidly assembly the titled subunit.

  DOI：

  10.1021/ol7025944
• 作为产物：
  描述：

  4-甲氧基溴苄 、 1-(tert-butyldimethylsilyloxy)-2,4-dimethylhex-5-en-3-ol 在 sodium hydride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 以95%的产率得到tert-butyl-[(2R,3S,4R)-3-[(4-methoxyphenyl)methoxy]-2,4-dimethylhex-5-enoxy]-dimethylsilane
  参考文献：
  名称：

  A Multifaceted Phosphate Tether:  Application to the C1−C14 Subunit of Dolabelides A−D

  摘要：

  A phosphate tether approach to the C1-14 subunit of dolabelide is described. The phosphate tether serves a multifaceted role mediating several processes, including (i) diastereotopic differentiation via RCM, (ii) selective CM by imparting Type III behavior to the exocyclic olefin, (iii) regioselective hydrogenation, and (iv) regioselective Pd(0)-catalyzed reductive opening of the bicyclic phosphate. Overall, this strategy uses orthogonal protecting- and leaving-group properties innate to phosphate esters to rapidly assembly the titled subunit.

  DOI：

  10.1021/ol7025944

文献信息

• 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.
• A Phosphate Tether-Mediated, One-Pot, Sequential Ring-Closing Metathesis/Cross-Metathesis/Chemoselective Hydrogenation Protocol
  作者：Phanindra K. M. Venukadasula、Rambabu Chegondi、Gregory M. Suryn、Paul R. Hanson

  DOI：10.1021/ol301007h

  日期：2012.5.18

  A versatile three-step, one-pot, sequential reaction protocol involving ring-closing metathesis, cross-metathesis, and chemoselective hydrogenation is reported. This phosphate tether-mediated process occurs without intermediate isolation, is chemoselective, and is governed by stereoelectronic properties innate to phosphate tethers, which ultimately act to preserve the integrity of the bisallylic, bicyclic phosphate for subsequent nucleophilic additions. Overall, this process can be used to efficiently generate advanced polyol synthons.