(E)-6-(tert-butyldiphenylsilyloxy)-3-methylhex-2-en-1-ol | 187336-22-7

• 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: (E)-6-(tert-butyldiphenylsilyloxy)-3-methylhex-2-en-1-ol
• 英文别名: (E)-6-((Tert-butyldiphenylsilyl)oxy)-3-methylhex-2-EN-1-OL；(E)-6-[tert-butyl(diphenyl)silyl]oxy-3-methylhex-2-en-1-ol
• CAS: 187336-22-7
• 化学式: C₂₃H₃₂O₂Si
• 分子量: 368.591
• InChiKey: KOWZZZBJFWAADM-LVZFUZTISA-N

物化性质

• 沸点：
  448.5±45.0 °C(Predicted)
• 密度：
  1.01±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.28
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 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：

  (E)-6-(tert-butyldiphenylsilyloxy)-3-methylhex-2-en-1-ol 在 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 42.0h， 生成 (E)-4-methyl-7-phenyl-heptan-4-ene-1-ol mesylate
  参考文献：
  名称：

  Catalytic Diastereoselective Polycyclization of Homo(polyprenyl)arene Analogues Bearing Terminal Siloxyvinyl Groups

  摘要：

  Highly diastereoselective polycyclization of homo(polyprenyl) arene analogues bearing terminal siloxyvinyl groups was catalyzed by tin(IV) chloride (10 mol %). The cyclizations of tert-butyldiphenylsilyl and triisopropylsilyl polyenol ethers gave 4 alpha(equatorial)- and 4 beta(axial)-siloxypolycycles as major isomers, respectively. The strong nucleophilicity of pro-C(9), a (6E) geometry, and a bulky silyl group effectively favored the 4 alpha-preference, whereas the weak nucleophilicity of pro-C(9), a (6Z)-geometry, and less steric hindrance of a silyl group favored the 4 beta-preference.

  DOI：

  10.1021/ol062378t
• 作为产物：
  描述：

  5-羟基-2-戊酮 在 咪唑 、 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (E)-6-(tert-butyldiphenylsilyloxy)-3-methylhex-2-en-1-ol
  参考文献：
  名称：

  通过闭环烯炔复分解作用的功能复分解催化剂：活性异遥爪聚合物的一锅法

  摘要：

  Enyne 闭环复分解已用于从商业（Ru-亚苄基）Grubbs 催化剂合成带有官能团的复分解催化剂。新的 Grubbs 型钌卡宾用于合成活性异遥爪 ROMP 聚合物，无需任何中间纯化。用单取代炔烃进行烯烃复分解，然后用烯丙基醚进行闭环复分解，为获得带有新官能团的复分解催化剂提供了有效途径。不同功能的亚苄基和亚烷基衍生物已经在一锅合成异远螯聚合物中进行了研究。

  DOI：

  10.1021/jacs.7b12805

文献信息

• Polyene substrates with unusual methylation patterns to probe the active sites of three catalytic antibodies
  作者：Geun Tae Kim、Marion Wenz、Jong Il Park、Jens Hasserodt、Kim D Janda

  DOI：10.1016/s0968-0896(01)00402-3

  日期：2002.5

  The first tetraene design (A) only contains trisubstituted double bonds and hence its synthesis starts from farnesol and tris-norgeraniol. The second tetraene design (B) is considered the more precise match to the inducing hapten that generated the antibody collections by exhibiting one disubstituted double bond and its synthesis utilizes a tris-norgeraniol derivative and a symmetrical bis-allylic alcohol

  描述了在甲基丙烯酸酯生物合成中与天然底物甲基化模式不同的两种四烯的合成，2,3-氧化角鲨烯，以及用三种催化抗体进行的检测。这些新颖的线性萜类结构的设计受三种催化抗体表征的初步结果支配。它们是通过模拟多环化的类固醇半抗原免疫而产生的，不需要添加抗马尔可夫尼可夫化合物或扩环。与在羊毛甾醇，环戊烯醇和β-amyrin生物合成中观察到的氧化角鲨烯环化相比，这种反应级联将代表更“原始”的形式，并且不需要角鲨烯中第三和第四异戊二烯单元的尾到尾连接。第一个四烯设计（A）仅包含三取代的双键，因此其合成从法尼醇和三-降冰片酚开始。第二个四烯设计（B）被认为与通过显示一个双取代的双键生成抗体集合的诱导半抗原更精确地匹配，并且其合成利用了tris-norgeraniol衍生物和对称的双烯丙基醇作为关键构件。色谱比较研究得出的结论是，如先前从角鲨烯衍生的底物中观察到的，目前研究的抗体还可以从两种底物产生单环产物。
• Asymmetric Construction of All-Carbon Quaternary Stereocenters by Chiral-Auxiliary-Mediated Claisen Rearrangement and Total Synthesis of (+)-Bakuchiol
  作者：Ken-ichi Takao、Shu Sakamoto、Marianne Touati、Yusuke Kusakawa、Kin-ichi Tadano

  DOI：10.3390/molecules171113330

  日期：——

  An asymmetric Claisen rearrangement using Oppolzer’s camphorsultam was developed. Under thermal conditions, a geraniol-derived substrate underwent the rearrangement with good stereoselectivity. The absolute configuration of the newly formed all-carbon quaternary stereocenter was confirmed by the total synthesis of (+)-bakuchiol from the rearrangement product.

  开发了使用 Oppolzer 的樟脑磺胺的不对称克莱森重排。在热条件下，香叶醇衍生的底物经历了具有良好立体选择性的重排。新形成的全碳四元立体中心的绝对构型通过从重排产物中全合成 (+)-补骨脂酚得到证实。
• Syntheses and Biological Evaluation of Costunolide, Parthenolide, and Their Fluorinated Analogues
  作者：Zhong-Jin Yang、Wei-Zhi Ge、Qiu-Ying Li、Yaxin Lu、Jian-Miao Gong、Bei-Jia Kuang、Xiaonan Xi、Haiting Wu、Quan Zhang、Yue Chen

  DOI：10.1021/acs.jmedchem.5b00915

  日期：2015.9.10

  Inspired by the biosynthesis of sesquiterpene lactones (SLs), herein we report the asymmetric total synthesis of the germacrane ring (24). The synthetic strategy features a selective aldol reaction between beta,gamma-unsaturated chiral sulfonylamide 15a and aldehyde 13, as well as the intramolecular alpha-alkylation of sulfone 21 to construct a 10-membered carbocylic ring. The key intermediate 24 can be used to prepare the natural products costunolide and parthenolide (PTL), which are the key precursors for transformation into other SLs. Furthermore, the described synthetic sequences are amenable to the total synthesis of SL analogues, such as trifluoro-methylated analogues 32 and 45. Analogues 32 and 45 maintained high activities against a series of cancer cell lines compared to their parent PTL and costunolide, respectively. In addition, 32 showed enhanced tolerance to acidic media compared with PTL. To our surprise, PTL and 32 showed comparable half-lives in rat plasma and in the presence of human liver microsomes.
• Functional Metathesis Catalyst Through Ring Closing Enyne Metathesis: One Pot Protocol for Living Heterotelechelic Polymers
  作者：Subhajit Pal、Fiorella Lucarini、Albert Ruggi、Andreas F. M. Kilbinger

  DOI：10.1021/jacs.7b12805

  日期：2018.3.7

  Enyne ring closing metathesis has been used to synthesize functional group carrying metathesis catalysts from a commercial (Ru-benzylidene) Grubbs' catalysts. The new Grubbs-type ruthenium carbene was used to synthesize living heterotelechelic ROMP polymers without any intermediate purification. Olefin metathesis with a mono substituted alkyne followed by ring closing metathesis with an allylic ether

  Enyne 闭环复分解已用于从商业（Ru-亚苄基）Grubbs 催化剂合成带有官能团的复分解催化剂。新的 Grubbs 型钌卡宾用于合成活性异遥爪 ROMP 聚合物，无需任何中间纯化。用单取代炔烃进行烯烃复分解，然后用烯丙基醚进行闭环复分解，为获得带有新官能团的复分解催化剂提供了有效途径。不同功能的亚苄基和亚烷基衍生物已经在一锅合成异远螯聚合物中进行了研究。
• Catalytic Diastereoselective Polycyclization of Homo(polyprenyl)arene Analogues Bearing Terminal Siloxyvinyl Groups
  作者：Muhammet Uyanik、Kazuaki Ishihara、Hisashi Yamamoto

  DOI：10.1021/ol062378t

  日期：2006.11.1

  Highly diastereoselective polycyclization of homo(polyprenyl) arene analogues bearing terminal siloxyvinyl groups was catalyzed by tin(IV) chloride (10 mol %). The cyclizations of tert-butyldiphenylsilyl and triisopropylsilyl polyenol ethers gave 4 alpha(equatorial)- and 4 beta(axial)-siloxypolycycles as major isomers, respectively. The strong nucleophilicity of pro-C(9), a (6E) geometry, and a bulky silyl group effectively favored the 4 alpha-preference, whereas the weak nucleophilicity of pro-C(9), a (6Z)-geometry, and less steric hindrance of a silyl group favored the 4 beta-preference.