(2'R,3'S)-<3'-(tert-butyldimethylsilyloxy)tetrahydropyran-2'-yl>ethanol | 125877-98-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (2'R,3'S)-<3'-(tert-butyldimethylsilyloxy)tetrahydropyran-2'-yl>ethanol
• 英文别名: 2-[(2R,3S)-3-[tert-butyl(dimethyl)silyl]oxyoxan-2-yl]ethanol
• CAS: 125877-98-7
• 化学式: C₁₃H₂₈O₃Si
• 分子量: 260.449
• InChiKey: JBNSRDYPVRCDQK-NEPJUHHUSA-N

物化性质

• 沸点：
  306.6±27.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.94
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2'R,3'S)-<3'-(tert-butyldimethylsilyloxy)tetrahydropyran-2'-yl>ethanol 在 咪唑 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium periodate 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 草酰氯 、 pyridine-SO3 complex 、 4 A molecular sieve 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 silica gel 、 L-Selectride 、 二异丁基氢化铝 、 二甲基亚砜 、 (+)-Weinsaeure-diethylester 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 生成 (R)-4-[((2S,3aR,7aR)-2-Benzyloxycarbonyl-hexahydro-furo[3,2-b]pyran-2-yl)-hydroxy-methyl]-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Synthesis and biological activity of dysiherbaine model compound

  摘要：

  Synthesis of dysiherbaine model compound 2 and its diastereomer 3 is described. The structurally simplified model compound 2, lacking the hydroxyl and N-methyl groups on the tetrahydropyran ring, induced convulsive behavior in mice upon intracerebral injections; (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00413-x
• 作为产物：
  描述：

  (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane 在 盐酸 、 sodium tetrahydroborate 、 二异丁基氢化铝 作用下， 以 甲醇 、 二甲基亚砜 为溶剂， 反应 11.0h， 生成 (2'R,3'S)-<3'-(tert-butyldimethylsilyloxy)tetrahydropyran-2'-yl>ethanol
  参考文献：
  名称：

  Ring-Closing Metathesis in the Synthesis of Large and Medium-Sized Oxacycles. Application to the Synthesis of Polyoxygenated Macrocycles

  摘要：

  Ring-closing olefin metathesis (RCM) catalyzed by Grubbs's ruthenium benzylidene complex 1 is applied to the synthesis of unsaturated rings ranging in size from seven to thirteen members in trans-fused polyether systems. Reaction occurs with great efficiency in the cyclization of oxepene and oxocene rings, but as ring size increases, yields drop. The influence of the final double bond position is also studied. Better yields and milder reaction conditions are observed when an additional oxygen atom is introduced on the diene. This feature has promoted the application of this reaction to the synthesis of polyoxygenated macrocycles (with sizes ranging from 15 to 21 members), with excellent results.

  DOI：

  10.1021/jo9901438

文献信息

• Bridging of macrodithionolactones to bicyclic systems. Synthesis and modeling of oxapolycyclic frameworks
  作者：K. C. Nicolaou、C. K. Hwang、B. E. Marron、S. A. DeFrees、E. A. Couladouros、Y. Abe、P. J. Carroll、J. P. Snyder

  DOI：10.1021/ja00164a026

  日期：1990.4

  A new reaction involving bridging of macrodithionolactones to bicyclic systems is described. A series of macrodiolides was prepared and converted to the requisite macrodithionolactones. The latter substrates were induced to undergo bridging across the macrocyclic ring by exposure to sodium naphthalenide, leading to stable bicyclic systems upon addition of methyl iodide. The mixed thioketals so obtained

  描述了一种涉及将大二硫醇内酯桥接到双环系统的新反应。制备了一系列大二内酯并将其转化为必需的大二硫代内酯。后一种底物通过暴露于萘化钠而被诱导跨大环桥接，从而在加入甲基碘后形成稳定的双环系统。通过除去硫，将如此获得的混合硫缩酮转化为许多饱和或不饱和双环或多环系统。桥接的立体化学遵循顺式和反式产物的相对能量，而不是大环的构象偏好。MM2 计算和 X 射线晶体结构测定证实了这一点
• Convergent synthesis of the BCDEFGHIJ-ring polyether core of gambieric acids, potent antifungal polycyclic ethers
  作者：Kazushi Sato、Makoto Sasaki

  DOI：10.1016/j.tet.2007.02.039

  日期：2007.6

  A convergent synthesis of the nonacyclic BCDEFGHIJ-ring polyether core of gambieric acids, potent antifungal polycyclic ether marine natural products, has been achieved. The present synthesis involved as key features: (i) convergent union of the BCD- and GHIJ-ring fragments through esterification, (ii) construction of the E-ring as a lactone form via reductive acetylation, (iii) stereoselective allylation

  已经完成了冈比亚酸的非环状BCDEFGHIJ环聚醚核（有效的抗真菌多环醚海洋天然产物）的会聚合成。本合成涉及关键特征：（i）通过酯化使BCD-和GHIJ-环片段收敛结合，（ii）通过还原性乙酰化将E-环构造成内酯形式，（iii）立体选择性烯丙基化以建立C26立体中心，和（iv）闭环易位反应，形成九元F环。
• Diastereoselective Ring-Closing Metathesis as a Means to Construct Medium-Sized Cyclic Ethers: Application to the Synthesis of a Photoactivatable Gambierol Derivative
  作者：Yu Onodera、Kazuaki Hirota、Yuto Suga、Keiichi Konoki、Mari Yotsu-Yamashita、Makoto Sasaki、Haruhiko Fuwa

  DOI：10.1021/acs.joc.6b01302

  日期：2016.9.16

  describes a concise synthesis of six- to eight-membered α,α′-substituted cyclic ethers by exploiting diastereoselective ring-closing metathesis (RCM) of 1,4-pentadien-3-yl ether derivatives. The RCM precursors could be efficiently prepared via a vinylation of the corresponding α-acetoxy ether derivatives using divinylzinc. Diastereoselective RCM of 1,4-pentadien-3-yl ether derivatives afforded a series

  本文介绍了通过利用1,4-戊二烯-3-基醚衍生物的非对映选择性闭环复分解（RCM）合成六至八元的α，α'-取代的环醚的方法。可以使用二乙烯基锌通过相应的α-乙酰氧基醚衍生物的乙烯基化来有效地制备RCM前体。1,4-戊二烯-3-基醚衍生物的非对映选择性RCM提供一系列具有中等至良好非对映选择性的六至八元α，α'-取代的环状醚。非对映选择性RCM的立体化学结果似乎取决于所锻造的环的结构。六元和七元环醚的非对映选择性似乎在很大程度上受动力学控制，而与催化剂的反应性无关，而八元环醚的催化活性可以控制。最后，将非对映选择性RCM化学方法用于合成生物素标记的甘比罗尔可光活化衍生物。
• Studies toward the Total Synthesis of Gambieric Acids, Potent Antifungal Polycyclic Ethers:  Convergent Synthesis of the CDEFG-Ring System
  作者：Kazushi Sato、Makoto Sasaki

  DOI：10.1021/ol050760k

  日期：2005.6.1

  [reaction: see text] A convergent synthetic route to the CDEFG-ring system of gambieric acids, potent antifungal polycyclic ether marine natural products, has been developed. The present synthesis features convergent union of the CD- and G-rings through esterification, formation of the E-ring as a lactone form, stereoselective allylation to set the C26 stereocenter, and ring-closing metathesis reaction

  [反应：见正文]已经开发了一种聚合的合成路线，该路线可将甘菊酸（有效的抗真菌多环醚海洋天然产物）制成CDEFG环系统。本合成的特征是CD和G环通过酯化会聚，E环以内酯形式形成，通过立体选择性烯丙基化来设置C26立体中心，以及闭环易位反应以构建九元F-环。戒指。
• Pd(II)-Catalyzed Cyclization to Ether and Its Application to the Synthesis of the trans-Fused Polyether Core
  作者：Yoshiro Hirai、Hajime Yokoyama、Satoshi Nakayama、Masayuki Murase、Masahiro Miyazawa、Seiji Yamaguchi

  DOI：10.3987/com-08-s(f)36

  日期：——

  We employed an iterative Pd(II)-catalyzed cyclization reaction to ether from tri-O-acetyl-D-glucal to synthesize trans-fused polyethers. This approach should be applicable to synthesize the core structure of marine ladder toxins.

  我们采用迭代 Pd(II) 催化的从三-O-乙酰基-D-葡糖醛到醚的环化反应合成反式稠合聚醚。该方法应适用于合成海洋阶梯毒素的核心结构。