(2S,3S)-3-Methyl-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-4-penten-2-ol | 125803-69-2

• 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)-3-Methyl-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-4-penten-2-ol
• 英文别名: (2S,3S)-1-tert-butyldiphenylsilanyloxy-3-methylpent-4-en-2-ol；(2S,3S)-1-[tert-butyl(diphenyl)silyl]oxy-3-methylpent-4-en-2-ol
• CAS: 125803-69-2
• 化学式: C₂₂H₃₀O₂Si
• 分子量: 354.565
• InChiKey: TXLABTCYHHQFFL-GHTZIAJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.75
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 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)-3-Methyl-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-4-penten-2-ol 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 、 三甲基溴硅烷 、 三丁基膦 、 Raney Ni (W-2) 、 四丁基氟化铵 、 双氧水 、 四氯化锡 、 溶剂黄146 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 lithium bromide 、 锌 作用下， 以 四氢呋喃 、 吡啶 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 (4R,5R,8S)-5-Hydroxy-4,8-dimethyl-9-decenyl acetate
  参考文献：
  名称：

  Synthetic study on tautomycin. Stereocontrolled synthesis of C(1)C(18) fragment using a strategy of selective reduction of spiroketal

  摘要：

  A stereocontrolled synthesis of C(1)-C(18) fragment of tautomycin is accomplished employing asymmetric crotylboration, selective reduction of spiroketal, and addition of crotylstannane as the key steps.

  DOI：

  10.1016/s0040-4039(00)74091-3
• 作为产物：
  描述：

  (Z)-2,2,11,11-tetramethyl-3,3,10,10-tetraphenyl-4,9-dioxa-3,10-disiladodec-6-ene 在 臭氧 、 三苯基膦 作用下， 生成 (2S,3S)-3-Methyl-1-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-4-penten-2-ol
  参考文献：
  名称：

  Total Synthesis of Tautomycin

  摘要：

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.

  DOI：

  10.1021/jo00121a026

文献信息

• 種選択的な電子伝達系の複合体ＩＩ阻害活性を有する新規アトペニン類縁体
  申请人：学校法人北里研究所

  公开号：JP2016121072A

  公开（公告）日：2016-07-07

  【課題】寄生虫に対する種選択性が高い、電子伝達系の複合体II阻害活性を有する新規化合物を提供することを課題とする。【解決手段】本発明は、式（I）：で表される化合物若しくはその塩、又はそれらの溶媒和物に関する。【選択図】なし

  The task is to provide a novel compound with high species selectivity against parasites and inhibitory activity on the complex II of the electron transfer system. The present invention relates to a compound represented by formula (I) or its salt, or a solvate thereof. No selection figure is provided.
• Studies on the Synthesis of (−)-Gymnodimine. Subunit Synthesis and Coupling
  作者：James D. White、Laura Quaranta、Guoqiang Wang

  DOI：10.1021/jo062396o

  日期：2007.3.1

  portion of gymnodimine was synthesized via Diels−Alder cycloaddition of a 1,2,3-trisubstituted diene to a symmetrical dienophile obtained from Meldrum's acid. Differentiation of carbonyl groups in the cycloadduct was made by an intramolecular reaction with a neighboring alcohol to form a γ-lactone. Linkage of the two subunits at C18−C19 was accomplished by using a B-alkyl Suzuki coupling in which a borane

  合成了海洋藻毒素（-）-gymnodimine的两个主要亚基。经由高立体选择性碘介导的带有双2,6-二氯苄基（DCB）醚的无环烯烃的环化反应，制备了代表毒素C10-C18的三取代四氢呋喃。在该过程中顺式-2，5-二取代的四氢呋喃的形成符合Bartlett和Rychnovsky提出的DCB基团的立体定向作用。通过将1,2,3-三取代的二烯与由麦德鲁姆酸制得的对称的亲二烯体进行狄尔斯-阿尔德环加成反应，合成了与裸草二胺的C1-C8，C19-C24部分相对应的环己烯亚基。通过与相邻醇的分子内反应以形成γ-内酯来进行环加合物中羰基的区分。E）-碘代烯烃连接在四氢呋喃区段的C16处。随后的转化将官能团定位在偶联的产物中，以用于将来的大环化事件，该事件将关闭裸草二胺的15元环。
• Mulzer, Johann; Schoellhorn, Bernd, Angewandte Chemie, 1990, vol. 102, # 4, p. 433 - 435
  作者：Mulzer, Johann、Schoellhorn, Bernd

  DOI：——

  日期：——
• Total Synthesis of Tautomycin
  作者：Masato Oikawa、Tohru Ueno、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1021/jo00121a026

  日期：1995.8

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.
• Synthetic study on tautomycin. Stereocontrolled synthesis of C(1)C(18) fragment using a strategy of selective reduction of spiroketal
  作者：Masato Oikawa、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1016/s0040-4039(00)74091-3

  日期：1993.7

  A stereocontrolled synthesis of C(1)-C(18) fragment of tautomycin is accomplished employing asymmetric crotylboration, selective reduction of spiroketal, and addition of crotylstannane as the key steps.