1-tert-butyldimethylsilyloxy-2-methylhex-5-ene | 565193-93-3

• 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: 1-tert-butyldimethylsilyloxy-2-methylhex-5-ene
• 英文别名: tert-Butyl(dimethyl){[(2S)-2-methylhex-5-en-1-yl]oxy}silane；tert-butyl-dimethyl-[(2S)-2-methylhex-5-enoxy]silane
• CAS: 565193-93-3
• 化学式: C₁₃H₂₈OSi
• 分子量: 228.45
• InChiKey: CHHACUQKXVUKIB-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.61
• 重原子数：
  15
• 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：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-tert-butyldimethylsilyloxy-2-methylhex-5-ene 在 咪唑 、 dimethyl sulfide borane 、 碘 、 三苯基膦 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 6-tert-butyldimethylsilyloxy-1-iodo-5-methylhexane
  参考文献：
  名称：

  通过有机硼烷合成埃博霉素A的研究。

  摘要：

  已经描述了通过有机硼烷合成埃坡霉素A的研究。已开发出一种从异戊烯醇大规模制备B-γ，γ-二甲基烯丙基亚砜基樟脑基硼烷的改进方法。与各种醛反应后，该试剂以高对映选择性提供相应的α，α-二甲基均烯丙基醇。已经证明了该试剂在合成埃博霉素的C1-C6亚基中的应用。或者，分子间和分子内不对称还原方案也已用于合成埃坡霉素A的C1-C6亚基。使用α-pine烯衍生的试剂合成埃坡霉素A的C7-C21片段，涉及不对称烷氧基烯丙基和巴豆基硼化也已经描述过了。

  DOI：

  10.1039/b508001k
• 作为产物：
  描述：

  (2R)-3-[[(叔丁基)二甲基硅烷基]氧基]-2-甲基丙酸甲酯 在 咪唑 、 dilithium tetrachlorocuprate 、 dimethyl sulfide borane 、 碘 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 1-tert-butyldimethylsilyloxy-2-methylhex-5-ene
  参考文献：
  名称：

  通过有机硼烷合成埃博霉素A的研究。

  摘要：

  已经描述了通过有机硼烷合成埃坡霉素A的研究。已开发出一种从异戊烯醇大规模制备B-γ，γ-二甲基烯丙基亚砜基樟脑基硼烷的改进方法。与各种醛反应后，该试剂以高对映选择性提供相应的α，α-二甲基均烯丙基醇。已经证明了该试剂在合成埃博霉素的C1-C6亚基中的应用。或者，分子间和分子内不对称还原方案也已用于合成埃坡霉素A的C1-C6亚基。使用α-pine烯衍生的试剂合成埃坡霉素A的C7-C21片段，涉及不对称烷氧基烯丙基和巴豆基硼化也已经描述过了。

  DOI：

  10.1039/b508001k

文献信息

• Total Synthesis of (+)-18-<i>epi</i>-Latrunculol A: Development of a Synthetic Route
  作者：Brett D. Williams、Amos B. Smith

  DOI：10.1021/jo501733m

  日期：2014.10.3

  The evolution of an enantioselective total synthesis of (+)-18-epi-latrunculol A, a congener of the marine-sponge-derived latrunculins A and B, is reported. Key steps include a late-stage Mitsunobu macrolactonization to construct the 16-membered macrolactone, a mild Carreira alkynylation to unite the northern and southern hemispheres, a diastereoselective, acid-mediated δ-hydroxy enone cyclization/equilibration

  报告了 (+)-18- epi -latrunculol A（海洋海绵衍生的 latrunculins A 和 B 的同系物）的对映选择性全合成的演变。关键步骤包括后期 Mitsunobu 大环内酯化以构建 16 元大环内酯、温和的 Carreira 炔基化以统一北半球和南半球、非对映选择性、酸介导的 δ-羟基烯酮环化/平衡序列，以及功能组-耐受交叉复分解以获得烯酮环化前体。
• Structure–activity relationship of α hormones, the mating factors of phytopathogen Phytophthora
  作者：Shylaja D. Molli、Jianhua Qi、Arata Yajima、Keisuke Shikai、Tadashi Imaoka、Tomoo Nukada、Goro Yabuta、Makoto Ojika

  DOI：10.1016/j.bmc.2011.12.015

  日期：2012.1

  The mating hormones alpha 1 and alpha 2 induce sexual reproduction of the phytopathogenic genus Phytophthora. To demonstrate the structural elements responsible to hormonal activity, 17 derivatives of alpha 1 and alpha 2 were synthesized and their hormonal activity (oospore-inducing activity) was evaluated. The terminal ester derivatives of alpha 1 (diacetate and dibenzoate) retained the hormonal activity, whereas a dicarbamate derivative completely suppressed the activity. Even monocarbamates showed weak activities; among them the 1-O-carbamate was less active than 16-O-carbamate, suggesting that the 1-OH group is a little more important than 16-OH. Dihydro, dehydro, and demethyl derivatives exhibited the minimum level of activity. Surviving activity of 15-epi-alpha 1 suggested a less importance of this stereochemistry. Contrary to alpha 1, not only the terminal diacetate derivative but also monoacetates of alpha 2 exhibited no or little activity. Among the monoacetates, 1-O-acetyl-alpha 2 exhibited little yet relatively better activity than the others. No activity was observed for mono- and dicarbamoyl derivatives of alpha 2. Dihydro alpha 2 with the saturated double bond lost most of the activity. These findings suggest that both the mating hormones alpha 1 and alpha 2 require most of the functional (hydroxyl, keto, and olefinic) groups they possess in their natural form for inducing the sexual reproduction of Phytophthora. (C) 2011 Elsevier Ltd. All rights reserved.
• Total Synthesis of (+)-18-<i>epi-</i>Latrunculol A
  作者：Brett D. Williams、Amos B. Smith

  DOI：10.1021/ol4021892

  日期：2013.9.6

  An enantioselective total synthesis of the cytotoxic latrunculin congener (+)-18-epi-latrunculol A has been achieved. Key steps in the synthetic route include an acid-mediated enone cyclization/equilibration sequence, a Carreira alkynylation, and a late-stage Mitsunobu macrolactonization to construct the macrolide skeleton.
• Stereoselective synthesis of the C7C21 segment of epothilone A via asymmetric alkoxyallyl- and crotylboration
  作者：P.Veeraraghavan Ramachandran、Bodhuri Prabhudas、Debarshi Pratihar、J.Subash Chandra、M.Venkat Ram Reddy

  DOI：10.1016/s0040-4039(03)00748-2

  日期：2003.5

  The synthesis of the C-7-C-21 fragment of epothilone A involving asymmetric alkoxyallyl- and crotylboration using alpha-pinene-derived reagents is described. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Studies towards the synthesis of epothilone A via organoboranes
  作者：P. Veeraraghavan Ramachandran、J. Subash Chandra、Bodhuri Prabhudas、Debarshi Pratihar、M.Venkat Ram Reddy

  DOI：10.1039/b508001k

  日期：——

  of epothilone A via organoboranes have been described. A modified procedure for the large-scale preparation of B-gamma,gamma-dimethylallyldiisopinocampheylborane from prenyl alcohol has been developed. This reagent, upon reaction with various aldehydes, provides the corresponding alpha,alpha-dimethylhomoallylic alcohols in high enantioselectivities. The application of this reagent for the synthesis of

  已经描述了通过有机硼烷合成埃坡霉素A的研究。已开发出一种从异戊烯醇大规模制备B-γ，γ-二甲基烯丙基亚砜基樟脑基硼烷的改进方法。与各种醛反应后，该试剂以高对映选择性提供相应的α，α-二甲基均烯丙基醇。已经证明了该试剂在合成埃博霉素的C1-C6亚基中的应用。或者，分子间和分子内不对称还原方案也已用于合成埃坡霉素A的C1-C6亚基。使用α-pine烯衍生的试剂合成埃坡霉素A的C7-C21片段，涉及不对称烷氧基烯丙基和巴豆基硼化也已经描述过了。