(2R,3S)-2-methyl-3-[(triethylsilyl)oxy]pentanal | 108692-66-6

• 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: (2R,3S)-2-methyl-3-[(triethylsilyl)oxy]pentanal
• 英文别名: (2R,3S)-2-methyl-3-triethylsilyloxypentanal
• CAS: 108692-66-6
• 化学式: C₁₂H₂₆O₂Si
• 分子量: 230.423
• InChiKey: OOQJYAGTLZENRF-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2-methyl-3-[(triethylsilyl)oxy]pentanal 在 吡啶 、 正丁基锂 、 氢氟酸 、 caesium carbonate 、 二异丙胺 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 10.17h， 生成 (5S,6R,7S)-5,7-dihydroxy-6-methyl-1-[N-(2-acetamidoethyl)thio]nonan-3-one
  参考文献：
  名称：

  Functional Characterization of a Dehydratase Domain from the Pikromycin Polyketide Synthase

  摘要：

  Metabolic engineering of polyketide synthase (PKS) pathways represents a promising approach to natural products discovery. The dehydratase (DH) domains of PKSs, which generate an alpha,beta-unsaturated bond through a dehydration reaction, have been poorly studied compared with other domains, likely because of the simple nature of the chemical reaction they catalyze and the lack of a convenient assay to measure substrate turnover. Herein we report the first steady-state kinetic analysis of a PKS DH domain employing LC MS/MS analysis for product quantitation. PikDH2 was selected as a model DH domain. Its substrate specificity and mechanism were interrogated with a systematic series of synthetic triketide substrates containing a nonhydrolyzable thioether linkage as well as by site-directed mutagenesis, evaluation of the pH dependence of the catalytic efficiency (V-max/K-M), and kinetic characterization of a mechanism-based inhibitor. These studies revealed that PikDH2 converts D-alcohol substrates to trans-olefin products. The reaction is reversible with equilibrium constants ranging from 1.2 to 2. Moreover, the enzyme activity is robust, and PikDH2 was used on a preparative scale for the chemoenzymatic synthesis of unsaturated triketide products. PikDH2 was shown to possess remarkably strict substrate specificity and is unable to turn over substrates that are epimeric at the beta-, gamma-, or delta-position. We also demonstrated that PikDH2 has a key ionizable group with a pK(a) of 7.0 and can be irreversibly inactivated through covalent modification by a mechanism-based inhibitor, which provides a foundation for future structural studies to elucidate substrate protein interactions.

  DOI：

  10.1021/jacs.5b02325
• 作为产物：
  描述：

  Triethyl-((S)-1-ethyl-2-methyl-but-3-enyloxy)-silane 在 二甲基硫 、 臭氧 作用下， 以 甲醇 为溶剂， 生成 (2R,3S)-2-methyl-3-[(triethylsilyl)oxy]pentanal
  参考文献：
  名称：

  β-烷基均烯丙基醇的非对映体和对映体选择性制备：Serricornin和corynomycolic酸的合成

  摘要：

  已经开发了一种新的有效的方法来制备四种可能的β-烷基均烯丙基醇1的立体异构体，该方法基于将亲核试剂非对映选择性加成到光学活性的α-烷基-β-三甲基甲硅烷基-β，γ-不饱和羰基化合物上。该反应的实用性通过天然存在的serrcornin和corynomycolic酸的合成证明。

  DOI：

  10.1016/s0040-4020(01)90583-6

文献信息

• Process for total synthesis of pladienolide B and pladienolide D
  申请人：Kanada Mikie Regina

  公开号：US20080021226A1

  公开（公告）日：2008-01-24

  [Problems to be Solved] To provide an effective process for total synthesis of pladienolide B and pladienolide D having excellent anti-tumor activity and to provide useful intermediates in the above-described process. [Measure for Solving the Problem] A process for producing a compound represented by Formula (11): wherein P 1 , P 7 , P 8 , P 9 and R 1 are the same as defined below, characterized by including reacting a compound represented by Formula (12): wherein P 7 means a hydrogen atom or a protecting group for hydroxy group; R 1 means a hydrogen atom or a hydroxy group, with a compound represented by Formula (13): wherein P 1 means a hydrogen atom or a protecting group for hydroxy group; P 8 means a hydrogen atom, an acetyl group or a protecting group for hydroxy group; P 9 means a hydrogen atom or a protecting group for hydroxy group; or P 8 and P 9 may form together a group represented by a formula: wherein R 5 means a phenyl group which may have a substituent, in the presence of a catalyst.

  解决的问题：提供一种有效的全合成过程，用于合成具有出色抗肿瘤活性的pladienolide B和pladienolide D，并在上述过程中提供有用的中间体。 解决问题的措施：一种制备由下式（11）表示的化合物的方法： 其中P1、P7、P8、P9和R1如下定义，其特征在于包括将由下式（12）表示的化合物与由下式（13）表示的化合物在催化剂存在下反应： 其中P7表示氢原子或羟基的保护基团；R1表示氢原子或羟基； 其中P1表示氢原子或羟基的保护基团；P8表示氢原子、乙酰基团或羟基的保护基团；P9表示氢原子或羟基的保护基团；或P8和P9可共同形成下式所示的基团： 其中R5表示可能具有取代基的苯基。
• 12 MEMBERED-RING MACROLACTAM DERIVATIVES
  申请人：Miyano Masayuki

  公开号：US20080312317A1

  公开（公告）日：2008-12-18

  There provided a 12-membered-ring macrolactam derivative having antitumor activity: A compound represented by Formula (1) or a salt thereof. In this Formula, R 1 is a hydrogen atom, a C 1-6 alkyl group, a C 1-6 alkylcarbonyl group or a C 6-14 arylcarbonyl group; R 2 is a hydrogen atom or a C 1-6 alkyl group; R 3 is a hydrogen atom or a hydroxyl group; R 4 is a hydrogen atom or a hydroxyl group; R 5 is a hydrogen atom or a C 1-6 alkyl group; R 6 is a hydrogen atom or a hydroxyl group; and R 7 is an acetyl group or the like.

  提供了一种具有抗肿瘤活性的12-成员环大环内酰胺衍生物：由化学式（1）表示的化合物或其盐。在该化学式中，R1是氢原子、C1-6烷基基团、C1-6烷基羰基基团或C6-14芳基羰基基团；R2是氢原子或C1-6烷基基团；R3是氢原子或羟基；R4是氢原子或羟基；R5是氢原子或C1-6烷基基团；R6是氢原子或羟基；R7是乙酰基或类似物。
• Total Synthesis of the Potent Antitumor Macrolides Pladienolide B and D
  作者：Regina M. Kanada、Daisuke Itoh、Mitsuo Nagai、Jun Niijima、Naoki Asai、Yoshiharu Mizui、Shinya Abe、Yoshihiko Kotake

  DOI：10.1002/anie.200604997

  日期：2007.6.4