(2S,3S)-1-<(tert-butyldimethylsilyl)oxy>-2-methylhex-5-en-3-ol | 106296-59-7

• 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,3S)-1-<(tert-butyldimethylsilyl)oxy>-2-methylhex-5-en-3-ol
• 英文别名: (2S,3S)-1-(tert-butyldimethylsilyloxy)-2-methylhex-5-en-3-ol；(2S,3S)-1-[(tert-butyldimethylsilyl)oxy]-2-methylhex-5-en-3-ol；(2S,3S)-1-[tert-butyl(dimethyl)silyl]oxy-2-methylhex-5-en-3-ol
• CAS: 106296-59-7
• 化学式: C₁₃H₂₈O₂Si
• 分子量: 244.45
• InChiKey: BGRZRKHPNBYWOY-RYUDHWBXSA-N

物化性质

• 沸点：
  283.3±33.0 °C(Predicted)
• 密度：
  0.877±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.58
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S)-1-<(tert-butyldimethylsilyl)oxy>-2-methylhex-5-en-3-ol 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 sodium hypochlorite 、 sodium chlorite 、 sodium periodate 、 sodium dihydrogenphosphate 、 四氧化锇 、 Hoveyda-Grubbs catalyst second generation 、 2-甲基-2-丁烯 、 2,2,6,6-四甲基哌啶氧化物 、 2,4,6-三氯苯甲酰氯 、 palladium 10% on activated carbon 、 水 、 氢气 、 1-羟基苯并三唑 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 二乙胺 、 N,N-二异丙基乙胺 、 tin(ll) chloride 、 potassium bromide 作用下， 以 1,4-二氧六环 、 乙醚 、 乙醇 、 二氯甲烷 、 水 、 乙酸乙酯 、 甲苯 、 乙腈 、 叔丁醇 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 47.0h， 生成 (5R,8R,9S,11R,13aS)-5-benzyl-9-(tert-butyldimethylsilyloxy)-8-methyl-11-((S)-1-methyl-6-oxoheptyl)-decahydro-12-oxa-3a,6-diazacyclopentacyclododecene-4,7,13-trione
  参考文献：
  名称：

  Acremolide B的立体异构体的权宜合成§

  摘要：

  已经开发了合成丙烯酰胺类脂肽肽的非常直接的策略。合成亮点包括交叉复分解以偶联C1-C7和C8-C12片段，酯化以引入二肽单元，大内酰胺化以构建大环内酯核心，以及两个立体选择性烯丙基化/丁酰化以控制C4的所有四个立体异构中心。 C1-C12聚丙烯酸酯片段。

  DOI：

  10.1021/jo1017487
• 作为产物：
  描述：

  (S)-3-(tert-butyldimethylsilyloxy)-2-methylpropionic acid methyl ester 在 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 作用下， 以 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 4.83h， 生成 (2S,3S)-1-<(tert-butyldimethylsilyl)oxy>-2-methylhex-5-en-3-ol
  参考文献：
  名称：

  Acremolide B的立体异构体的权宜合成§

  摘要：

  已经开发了合成丙烯酰胺类脂肽肽的非常直接的策略。合成亮点包括交叉复分解以偶联C1-C7和C8-C12片段，酯化以引入二肽单元，大内酰胺化以构建大环内酯核心，以及两个立体选择性烯丙基化/丁酰化以控制C4的所有四个立体异构中心。 C1-C12聚丙烯酸酯片段。

  DOI：

  10.1021/jo1017487

文献信息

• Total Synthesis of (−)-Rhizopodin
  作者：Stephen M. Dalby、Jake Goodwin-Tindall、Ian Paterson

  DOI：10.1002/anie.201301978

  日期：2013.6.17

  Core assembly: The total synthesis of the myxobacterial metabolite rhizopodin, a potent actin‐binding anticancer agent, has been achieved. The modular synthesis utilizes a common C1–C22 monomeric unit to assemble the dimeric 38‐membered macrodiolide core, which was elaborated by a bidirectional boron‐mediated aldol reaction to install the characteristic side‐chains. The final global deprotection was

  核心组装：已经完成了一种强效的肌动蛋白结合抗癌药，即粘细菌代谢产物根瘤菌素的全合成。模块化合成利用一个常见的C1-C22单体单元组装二聚体38元大分子二醇核，这是通过双向硼介导的羟醛缩合反应进行了详细说明，以安装特征性的侧链。最终的整体脱保护主要取决于C16 / C16'处甲硅烷基保护基的正确选择。
• Catalytic Enantioselective and Catalyst-Controlled Diastereofacial-Selective Additions of Allyl- and Crotylboronates to Aldehydes Using Chiral Brønsted Acids
  作者：Vivek Rauniyar、Dennis G. Hall

  DOI：10.1002/anie.200504432

  日期：2006.4.3
• A More Comprehensive and Highly Practical Solution to Enantioselective Aldehyde Crotylation
  作者：Hyunwoo Kim、Stephen Ho、James L. Leighton

  DOI：10.1021/ja200712f

  日期：2011.5.4

  The enantioselective crotylation of aldehydes with 1,2-diaminochlorocrotylsilane reagents is effectively catalyzed by Sc(OTf)(3). The one significant limitation on the utility of these reagents - substrate scope - has thus been addressed. The net result is the most comprehensive and highly practical method for enantioselective aldehyde crotylation yet advanced.
• Asymmetric synthesis using tartrate ester modified allylboronates. 2. Single and double asymmetric reactions with alkoxy-substituted aldehydes
  作者：William R. Roush、Lee K. Hoong、Michelle A. J. Palmer、Julie A. Straub、Alan D. Palkowitz

  DOI：10.1021/jo00300a032

  日期：1990.6
• N,N'-Bis(2,2,2-trifluoroethyl)-N,N'-ethylenetartramide: An Improved Chiral Auxiliary for the Asymmetric Allylboration Reaction
  作者：William R. Roush、Paul T. Grover

  DOI：10.1021/jo00117a036

  日期：1995.6

  N,N-Bis(2,2,2-trifluoroethyl)-N,N'-ethylenetartramide (8), synthesized by a simple four-step sequence from ethylenediamine and benzylidenetartaric acid, was designed in anticipation that the derived allylboronates 9-11 would display enhanced reactivity owing to the inductive effect of the N-trifluoroethyl substituents that would increase the Lewis acidity of the boron atom of the B-allyl-1,3,2-dioxaborolanes. Reagents 9-11 were synthesized by transesterification of 8 with the crystalline and easily purified allylboronate diethanolamine complexes 13, 19, and 25. Allylboronate 9 is ca. 100-fold more reactive than 6 and is also substantially more useful than the previously reported allyboronate 4, which suffers from very poor solubility in toluene at -78 degrees C. Most importantly, allylboronates 9-11 are significantly more enantioselective than the parent tartrate allylboronates 1-3 and rank among the most highly enantioselective allylboron reagents yet reported. Reactions of 9-11 with aldehydes are performed in THF at- -78 or -55 degrees C for 5-12 h periods. The enantioselectivity realized in reactions with achiral aldehydes is 92-95% ee (Table 2), and excellent diastereoselectivity is achieved in double asymmetric reactions with chiral aldehydes 15a, 15b, and 33 (Tables 3 and 4). For example, 16 and 28 are now available with a minimum selectivity of 92% from reactions of 15a and 15b with allylboronate 9, while the crotylboration products 29, 30, and 31 are available with a minimum selectivity of 90% (usually greater than or equal to 95%) from reactions of 15a and 15b with crotylboronates 10 and 11; the fourth isomer, 32a, is available with 83% selectivity. Chiral reagents 9-11 thus appear well suited for application to complex problems in organic synthesis.