(4Z)-4-methoxy-2,2,7,7,8,8-hexamethyl-3,6-dioxa-2,7-disila-non-4-ene | 150811-51-1

• 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: (4Z)-4-methoxy-2,2,7,7,8,8-hexamethyl-3,6-dioxa-2,7-disila-non-4-ene
• 英文别名: (Z)-2-(tert-Butyldimethylsiloxy)-1-methoxy-1-(trimethylsiloxy)ethene；tert-butyl-[(Z)-2-methoxy-2-trimethylsilyloxyethenoxy]-dimethylsilane
• CAS: 150811-51-1
• 化学式: C₁₂H₂₈O₃Si₂
• 分子量: 276.524
• InChiKey: QUOWGEYWWFWIMF-KHPPLWFESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S,5S)-4,5-Dimethoxymethyl-2-(N-p-methoxyphenyl)iminomethyl-2-methyl-1,3-dioxolane 、 (4Z)-4-methoxy-2,2,7,7,8,8-hexamethyl-3,6-dioxa-2,7-disila-non-4-ene 在 Amberlyst(R) 15 DRY 作用下， 以 二氯甲烷 为溶剂， 反应 14.0h， 以90%的产率得到
  参考文献：
  名称：

  A Cation-exchange Resin Promoted Imino Aldol Reaction, Leading to the Synthesis of 2-Isocephem and 2-Oxa-isocephem

  摘要：

  在阳离子交换树脂的作用下，烯酮硅基乙醛与手性亚胺 1 的氨基醛醇反应顺利进行，以良好的收率和较高的二乙醚选择性得到了β-氨基酯，随后的官能团转化提供了 2-isocephem 和 2-oxa-isocephem β-内酰胺抗生素的正式合成。

  DOI：

  10.1246/cl.2004.1394
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.42h， 生成 (4Z)-4-methoxy-2,2,7,7,8,8-hexamethyl-3,6-dioxa-2,7-disila-non-4-ene
  参考文献：
  名称：

  [EN] METHODS FOR THE PRODUCTION OF SORANGICINS AND THEIR ANALOGUES
  [FR] PROCÉDÉS DE PRODUCTION DE SORANGICINES ET DE LEURS ANALOGUES

  摘要：

  The present invention describes a novel synthetic pathway for the production of sorangicins and their analogues according to a compound of formula (I), wherein the variables R1, R2, R3, R4, and R5are defined in the description, providing the key building blocks according to formulae A, B, C, D, E, and F, which are described in the description, in coupling reactions and a final cyclisation to form a compound of formula (I). The compounds produced according to the present invention are useful as antibiotics.

  公开号：

  WO2023057645A1

文献信息

• Lewis Base Activation of Lewis Acids: Catalytic, Enantioselective Addition of Glycolate-Derived Silyl Ketene Acetals to Aldehydes
  作者：Scott E. Denmark、Won-jin Chung

  DOI：10.1021/jo8006539

  日期：2008.6.1

  A catalytic system involving silicon tetrachloride and a chiral, Lewis basic bisphosphoramide catalyst is effective for the addition of glycolate-derived silyl ketene acetals to aldehydes. It was found that the sense of diastereoselectivity could be modulated by changing the size of the substituents on the silyl ketene acetals. In general, the trimethylsilyl ketene acetals derived from methyl glycolates

  涉及四氯化硅和手性路易斯碱性双磷酰胺催化剂的催化体系可有效地将乙醇酸衍生的甲硅烷基烯酮缩醛添加到醛中。发现可以通过改变甲硅烷基烯酮缩醛上取代基的大小来调节非对映选择性。一般情况下，三甲基甲硅烷烯酮缩醛选自甲基甘醇酸酯衍生的与α-氧气的大型保护基提供对映体富集的α，β二羟基酯具有高顺式-diastereoselectivity，而叔丁基二烯酮缩醛从α-笨重的酯衍生的甲氧基乙酸提供对映体富集的α，高β二羟基酯抗-diastereoselecitvity。
• Highly selective enolization method for heteroatom substituted esters; its application to the ireland ester enolate claisen rearrangement
  作者：Kouji Hattori、Hisashi Yamamoto

  DOI：10.1016/s0040-4020(01)81109-1

  日期：1994.3

  A method for the stereoselective synthesis of silyl ketene acetals from α-siloxy esters, β-hydroxy esters, and α-amino esters is described. Internal quench with excess trimethylsilyl chloride of the lithium enolate at −100 °C, which is generated using a hindered base, LTMP, leads to the selective formation of E-silyl ketene acetal. In contrast, the deprotonation at −100 °C using LHMDS in THF-HMPA (4:1)

  描述了一种由α-甲硅烷氧基酯，β-羟基酯和α-氨基酯立体选择性合成甲硅烷基烯酮缩醛的方法。使用受阻碱LTMP在-100°C下用过量的烯醇锂的三甲基甲硅烷基氯进行内部淬灭，可选择性地形成E-甲硅烷基乙烯酮缩醛。相反，使用LHMDS在THF-HMPA（4：1）中在-100°C进行去质子化，然后用叔丁基二甲基甲硅烷基氯进行处理，可以选择性地得到Z-甲硅烷基烯酮缩醛。该方法可用于爱尔兰酯烯酸酯克莱森重排的立体选择反应。
• Lewis Base Activation of Lewis Acids: Catalytic Enantioselective Glycolate Aldol Reactions
  作者：Scott E. Denmark、Won-jin Chung

  DOI：10.1002/anie.200705499

  日期：2008.2.22
• Asymmetric Total Synthesis of TaxolR
  作者：Teruaki Mukaiyama、Isamu Shiina、Hayato Iwadare、Masahiro Saitoh、Toshihiro Nishimura、Naoto Ohkawa、Hiroki Sakoh、Koji Nishimura、Yu-ichirou Tani、Masatoshi Hasegawa、Koji Yamada、Katsuyuki Saitoh

  DOI：10.1002/(sici)1521-3765(19990104)5:1<121::aid-chem121>3.3.co;2-f

  日期：1999.1.4
• Highly selective generation and application of (E)- and (Z)-silyl ketene acetals from .alpha.-hydroxy esters
  作者：Kouji Hattori、Hisashi Yamamoto

  DOI：10.1021/jo00072a005

  日期：1993.9

  A method for the stereoselective synthesis of silyl ketene acetals from a-hydroxy esters is described. Internal quench with excess TMSCI of the lithium enolate at -100-degrees-C, which is generated using a hindered base, LTMP, leads to the selective formation of (E)-silyl ketene acetal. In contrast, the deprotonation at -100-degrees-C using LHMDS in THF-HMPA (4:1), followed by treatment with tert-butyldimethylsilyl chloride affords the (Z)-silyl ketene acetal selectively. The method can be applied to the stereoselective reaction of the Ireland ester enolate Claisen rearrangement and aldol synthesis.