(3R,4R)-6-<<(tert-butyldimethyl)silyl>oxy>-4-hydroxy-3-methylhex-1-ene | 121099-21-6

• 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: (3R,4R)-6-<<(tert-butyldimethyl)silyl>oxy>-4-hydroxy-3-methylhex-1-ene
• 英文别名: (3R,4R)-3-methyl-6-<(tert-butyldimethylsilyl)oxy>-1-hexen-4-ol；(3R,4R)-6-{[(tert-butyldimethyl)silyl]oxy}-4-hydroxy-3-methylhex-1-ene；(3R,4R)-1-(tert-butyldimethylsilyloxy)-4-methylhex-5-en-3-ol；(3R,4R)-3-methyl-6-[(tert-butyldimethylsilyl)oxy]-1-hexen-4-ol；(3R,4R)-1-[tert-butyl(dimethyl)silyl]oxy-4-methylhex-5-en-3-ol
• CAS: 121099-21-6
• 化学式: C₁₃H₂₈O₂Si
• 分子量: 244.45
• InChiKey: GJHUADNGYVGMIX-VXGBXAGGSA-N

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：

  (3R,4R)-6-<<(tert-butyldimethyl)silyl>oxy>-4-hydroxy-3-methylhex-1-ene 在 lithium hydroxide 、 四丁基氟化铵 、 sodium hydride 、 caesium carbonate 、 APTS 、 sodium chloride 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 乙腈 为溶剂， 反应 38.5h， 生成 2-[(2R,4S)-2-[(2R)-but-3-en-2-yl]-6-oxooxan-4-yl]acetic acid
  参考文献：
  名称：

  根瘤菌素全合成方法：内酯核心的对映选择性制备

  摘要：

  报道了抗肿瘤大环内酯药物rhizoxin的C1 - C10内酯核心的构建。该策略基于使用Brown烯基化反应建立C7和C8的不对称中心。在内酯化步骤中控制了C5的不对称碳，最终在C5处形成了赤道链。C3和C9的同族化反应分别通过Wadsworth-Emmons反应和Takai反应实现。

  DOI：

  10.1055/s-2001-14601
• 作为产物：
  描述：

  3-(叔丁基二甲基硅氧)丙醇 在 正丁基锂 、 三氟化硼乙醚 、 potassium tert-butylate 、 三氧化硫吡啶 、 三乙胺 、 (-)-B-methoxydiisopinocampheylborane 作用下， 以 四氢呋喃 、 正己烷 、 二甲基亚砜 为溶剂， 反应 4.17h， 生成 (3R,4R)-6-<<(tert-butyldimethyl)silyl>oxy>-4-hydroxy-3-methylhex-1-ene
  参考文献：
  名称：

  Allyltitanates in Stereospecific Additions to Chiral δ-Lactol:  Efficient Enantioselective Route to a Potential Precursor of the C1−C9 Portion of Tylonolide

  摘要：

  The Hoppe reaction, which is an allylation reaction of aldehydes using an optically active titanated crotyl carbamate intermediate generated from the corresponding N,N-diisopropyl crotyl carbamate with n-BuLi/(-)-sparteine, was in most cases applied to achiral aldehydes. In this work an extension of this reaction is reported using a racemic gamma-alkoxy allyltitanate (17) and an optically active aldehyde (16) to deliver in good yield the anti adduct 18 as the major isomer. When the corresponding delta-lactol 24 was used in place of aldehyde 16, the anti adduct 25 was obtained in 94% yield as the only product. Structural modifications effected on 25 delivered aldehyde 28 which was in turn submitted to a second allylation reaction in the presence of the optically active titanated crotyl carbamate 2, prepared as described by Hoppe from crotyl carbamate 1, to conduct to compound 29 in 80% yield. This derivative corresponds to a potential precursor of the C1-C9 portion of Tylonolide, aglycon of Tylosin (4).

  DOI：

  10.1021/jo9807722

文献信息

• Asymmetric synthesis using diisopropyl tartrate modified (E)- and (Z)-crotylboronates: preparation of the chiral crotylboronates and reactions with achiral aldehydes
  作者：William R. Roush、Kaori Ando、Daniel B. Powers、Alan D. Palkowitz、Ronald L. Halterman

  DOI：10.1021/ja00173a023

  日期：1990.8

  Crotylboronates undergo highly diastereo- and enantioselective reactions with aliphatic (linear or α-monobranched; 72-91% ee), aromatic and α,β-unsaturated aldehydes (55-74% ee). The reaction diastereoselectivity closely parallels the reagent isomeric purity especially for reactions performed at −78 o C. The enantioselectivity is best in toluene for all substrates except benzaldehyde where best results

  巴豆基硼酸酯与脂肪族（线性或 α-单支链；72-91% ee）、芳香族和 α,β-不饱和醛（55-74% ee）发生高度非对映选择性和对映选择性反应。反应的非对映选择性与试剂异构体纯度密切相关，特别是对于在 -78 o C 下进行的反应。对所有底物的对映选择性在甲苯中最佳，但苯甲醛除外，因为苯甲醛在 THF 中获得最佳结果。本研究中合成的 14 种高烯丙醇中有 9 种的相对和绝对立体化学是通过与 Sharpless 不对称环氧化制备的环氧醇的相关性来确定的
• Enantioselective synthesis using diisopropyl tartrate modified (E)- and (Z)-crotylboronates: Reactions with achiral aldehydes
  作者：William R. Roush、Kaori Ando、Daniel B. Powers、Ronald L. Halterman、Alan D. Palkowitz

  DOI：10.1016/s0040-4039(00)80816-3

  日期：1988.1

  The reactions of diisopropyl tartrate modified( E)- and (Z)-crotylboronates with representative achiral aldehydes are described. Enantioselectivity ranges from 55–91% e.e. depending on the aldehyde employed.

  描述了酒石酸二异丙酯改性的（E）-和（Z）-巴豆基硼酸酯与代表性的非手性醛的反应。对映选择性范围为55–91％ee，具体取决于所用的醛。
• Spiroacetal Formation through Telescoped Cycloaddition and Carbon-Hydrogen Bond Functionalization: Total Synthesis of Bistramide A
  作者：Xun Han、Paul E. Floreancig

  DOI：10.1002/anie.201406819

  日期：2014.10.6

  Spiroacetals can be formed through a one‐pot sequence of a hetero‐Diels–Alder reaction, an oxidative carbon–hydrogen bond cleavage, and an acid treatment. This convergent approach expedites access to a complex molecular subunit which is present in numerous biologically active structures. The utility of the protocol is demonstrated through its application to a brief synthesis of the actin‐binding cytotoxin

  螺缩醛可以通过杂狄尔斯-阿尔德反应、氧化碳氢键断裂和酸处理的一锅顺序形成。这种趋同方法加快了对存在于众多生物活性结构中的复杂分子亚基的访问。该协议的实用性通过其在肌动蛋白结合细胞毒素双酰胺 A 的简要合成中的应用得到证明。
• SYNTHESIS OF (S,S)-DIISOPROPYL TARTRATE (E)-CROTYLBORONATE AND ITS REACTION WITH ALDEHYDES: (2R,3R,4R)-1,2-DIDEOXY-2-ETHENYL-4,5-O-(1-METHYLETHYLIDENE)-XYLITOL
  作者：Sun, Huikai、Roush, William R.

  DOI：10.15227/orgsyn.088.0181

  日期：——
• Synthesis of Bistramide A
  作者：Alexander V. Statsuk、Dong Liu、Sergey A. Kozmin

  DOI：10.1021/ja046588h

  日期：2004.8.1

  We have developed an efficient and highly stereocontrolled synthesis of bistramide A, a selective activator of protein kinase C isotype delta. Our synthetic strategy featured a novel bidirectional approach for spiroketal construction based on the ring-opening/cross-metathesis sequence employing a highly strained cyclopropenone acetal. The synthesis afforded the final target with the longest linear sequence of 15 steps and provided unambiguous structural determination of bistramide A, including assignment of the previously unknown C(37) stereochemistry.