(Z)-2-[3-(Trimethylsilyl)-2-propynylidene]-cyclopentanone | 128878-87-5

• 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: (Z)-2-[3-(Trimethylsilyl)-2-propynylidene]-cyclopentanone
• 英文别名: (2Z)-2-(3-trimethylsilylprop-2-ynylidene)cyclopentan-1-one
• CAS: 128878-87-5
• 化学式: C₁₁H₁₆OSi
• 分子量: 192.333
• InChiKey: NQSQFBMOHALGAH-YFHOEESVSA-N

物化性质

• 沸点：
  251.2±20.0 °C(Predicted)
• 密度：
  1.025±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.55
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-2-[3-(Trimethylsilyl)-2-propynylidene]-cyclopentanone 在 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 、 水 、 巯基乙酸甲酯 、 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 17.0h， 生成 1-(3-Methoxy-2-phenylethynyl-cyclopent-1-enyl)-3-trimethylsilanyl-prop-2-yn-1-ol
  参考文献：
  名称：

  Two distinct epoxide ring opening pathways in a monocyclic model system of the kedarcidin chromophore

  摘要：

  Two monocyclic model compounds 2 and 3 were synthesized from (Z)-ketoeneyne 5 for studying the epoxide ring opening pathways related to activation of the kedarcidin chromophore (1). The solvent-derived S(N)1 products 8a,b and 9a,b were formed from 2 and 3 in MeOH while the S(N)2 products 10a,b were produced from 2 and 3 with methyl thioglycolate in buffer (pH 7.0)-iPrOH; the latter reaction may provide a new scenario for bioreductive activation of the kedarcidin chromophore via an S(N)2 attack of thiol at the propargylic carbon atom. (C) 1998 Elsevier Science Ltd. Ail rights reserved.

  DOI：

  10.1016/s0040-4039(98)00664-9
• 作为产物：
  描述：

  (Z)-2-(hydroxymethylene)cyclopentan-1-one 在 copper(l) iodide 、 四(三苯基膦)钯 、 叔丁基锂 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 0.59h， 生成 (Z)-2-[3-(Trimethylsilyl)-2-propynylidene]-cyclopentanone
  参考文献：
  名称：

  Stereoselective synthesis of (Z)-ketoeneynes via Pd(0)-Cu(I)-catalyzed cross-coupling of (Z)-ketoenol triflate with 1-alkynes

  摘要：

  A general and stereoselective synthesis of (Z)-ketoeneynes 9 and 11a-f was established by using a Pd(O)-Cu(I)-catalyzed cross-coupling of the labile (Z)-ketoenol triflate 3 with 1-alkynes under carefully controlled reaction conditions. Isomerization of the coupling products into the more stable (E)-ketoeneynes 8 and 12a-f was observed and could be minimized by earring out the coupling reaction in CH3CN at low temperature using Et3N as the base. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00610-8

文献信息

• Stereoselective aldol reaction of α-seleno carbonyl compounds: preparation of (Z)-α,β-unsaturated carbonyl compounds
  作者：Shuichi Nakamura、Toshinobu Hayakawa、Tatsuya Nishi、Yoshihiko Watanabe、Takeshi Toru

  DOI：10.1016/s0040-4020(01)00606-8

  日期：2001.7

  titanium enolates of α-seleno esters in the presence of Ph3P or Ph3PO gave the products with high stereoselectivity favoring the syn isomers. Reaction of α-seleno ketones with TiCl4 in the presence of 2 equiv. of Et3N, and subsequently with aldehydes, gave the aldol products with high syn selectivity. The stereoselectivity in the aldol reaction of 3-pentanone also increased by using an excess amount of Et3N

  α-硒基酯的烯醇化物的钛的pH值的存在醛醇缩合反应3 P或博士3 PO，得到的产品具有高的立体选择性有利于顺式异构体。在2当量存在下，α-硒代酮与TiCl 4的反应。Et 3 N，然后与醛混合，得到具有高顺式选择性的醛醇产物。通过使用过量的Et 3 N ，3-戊酮的醛醇缩合反应中的立体选择性也增加了。这样从α-硒代羰基化合物获得的醛醇产物可以立体定向转化为（Z）-α，β-不饱和羰基化合物用吡啶处理。（Z）-亚烷基环戊酮仅通过在黑暗中用Et 3 N处理顺-醛醇产物而形成。
• Synthetic studies on the compounds related to neocarzinostatin chromophore. 1. Synthesis of the acyclic (E)- and (Z)-dienediyne systems
  作者：Kazuhiko Nakatani、Katsuko Arai、Noriaki Hirayama、Fuyuhiko Matsuda、Shiro Terashima

  DOI：10.1016/s0040-4020(01)88124-2

  日期：——

  The stereo-defined (E)- and (Z)-dienediyne systems related to neocarzinostatin chromophore (1) could be prepared by the coupling reaction of (E)- and (Z)-enol triflates with optically active acetylynes hearing the correct absolute stereochemistries as found in 1. Comparison of cytotoxic level of the (E)- and (Z)-dienediyne diols (32 and 33) revealed that the stereochemistry of exo-trisubstituted double bond might have a posibility to control the cytotoxicity of the acyclic analogues related to I.
• Synthesis and cytotoxicity of the acyclic (E)- and (Z)-dienediyne systems related to neocarzinostatine chromophore
  作者：Kazuhiko Nakatani、Katsuko Arai、Noriaki Hirayama、Fuyuhiko Matsuda、Shiro Terashima

  DOI：10.1016/0040-4039(90)80218-b

  日期：1990.1
• NAKATANI, KAZUHIKO;ARAI, KATSUKO;HIRAYAMA, NORIAKI;MATSUDA, FUYUHIKO;TERA+, TETRAHEDRON LETT., 31,(1990) N6, C. 2323-2326
  作者：NAKATANI, KAZUHIKO、ARAI, KATSUKO、HIRAYAMA, NORIAKI、MATSUDA, FUYUHIKO、TERA+

  DOI：——

  日期：——
• Two distinct epoxide ring opening pathways in a monocyclic model system of the kedarcidin chromophore
  作者：Wei-Min Dai、Jinlong Wu、Anxin Wu

  DOI：10.1016/s0040-4039(98)00664-9

  日期：1998.6

  Two monocyclic model compounds 2 and 3 were synthesized from (Z)-ketoeneyne 5 for studying the epoxide ring opening pathways related to activation of the kedarcidin chromophore (1). The solvent-derived S(N)1 products 8a,b and 9a,b were formed from 2 and 3 in MeOH while the S(N)2 products 10a,b were produced from 2 and 3 with methyl thioglycolate in buffer (pH 7.0)-iPrOH; the latter reaction may provide a new scenario for bioreductive activation of the kedarcidin chromophore via an S(N)2 attack of thiol at the propargylic carbon atom. (C) 1998 Elsevier Science Ltd. Ail rights reserved.