5-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-cyclohex-2-en-1-one | 943448-07-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-cyclohex-2-en-1-one
• 英文别名: 5-[2-[Tert-butyl(dimethyl)silyl]oxyethyl]cyclohex-2-en-1-one；5-[2-[tert-butyl(dimethyl)silyl]oxyethyl]cyclohex-2-en-1-one
• CAS: 943448-07-5
• 化学式: C₁₄H₂₆O₂Si
• 分子量: 254.445
• InChiKey: HHXORWCMSNVJBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 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：

  5-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-cyclohex-2-en-1-one 在 tris(dibenzylideneacetone)dipalladium (0) 1,1'-双(二苯基膦)二茂铁 、 羟胺 、 四丁基碘化铵 、 四丁基高碘酸铵 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 甲醇 、 正己烷 、 丙酮 为溶剂， 反应 6.5h， 生成 10-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-2-oxa-3-aza-tricyclo[6.3.1.0^3,9]dodec-8(12)-en-4-one
  参考文献：
  名称：

  An Approach to the Synthesis of Stenine

  摘要：

  A type 2 N-acylnitroso intramolecular Diels-Alder reaction followed by reductive N-O bond cleavage formed the B and C rings of the Stemona alkaloid stenine. Further elaboration provided the functionalized tricyclic core.

  DOI：

  10.1021/ol070397c
• 作为产物：
  描述：

  2-(1,4-dioxaspiro[4.5]dec-7-yl)malonic acid dimethyl ester 在 tris(dibenzylideneacetone)dipalladium (0) 2,2,6,6-四甲基哌啶 、 盐酸 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 正丁基锂 、 碳酸二稀丙酯 、 水 、 三乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 、 二甲基亚砜 、 乙腈 为溶剂， 反应 37.0h， 生成 5-[2-(tert-butyl-dimethyl-silanyloxy)-ethyl]-cyclohex-2-en-1-one
  参考文献：
  名称：

  An Approach to the Synthesis of Stenine

  摘要：

  A type 2 N-acylnitroso intramolecular Diels-Alder reaction followed by reductive N-O bond cleavage formed the B and C rings of the Stemona alkaloid stenine. Further elaboration provided the functionalized tricyclic core.

  DOI：

  10.1021/ol070397c

文献信息

• Catalytic Enantioselective Conjugate Allylation of Unsaturated Methylidene Ketones
  作者：Laura A. Brozek、Joshua D. Sieber、James P. Morken

  DOI：10.1021/ol102982b

  日期：2011.3.4

  The use of unsaturated methylidene ketones in catalytic conjugate allylations allows a significant expansion in substrate scope and, with appropriate chiral ligands, occurs in a highly enantioselective fashion.

  在催化共轭烯丙基化反应中使用不饱和亚甲基酮可以显着扩大底物范围，并且与适当的手性配体一起以高度对映选择性的方式发生。
• Regioselective Iridium-Catalyzed Asymmetric Monohydrogenation of 1,4-Dienes
  作者：Jianguo Liu、Suppachai Krajangsri、Thishana Singh、Giulia De Seriis、Napasawan Chumnanvej、Haibo Wu、Pher G. Andersson

  DOI：10.1021/jacs.7b06829

  日期：2017.10.18

  A highly efficient regio- and enantioselective monohydrogenation of 1,4-dienes has been realized using an iridium catalyst with a chiral N,P-ligand under mild conditions. The substrate scope was studied and included both unfunctionalized as well as functionalized substituents on the meta- or para-position. Substrates having substituents with functionalities such as silyl protected alcohols or ketals

  使用带有手性 N,P-配体的铱催化剂在温和条件下实现了 1,4-二烯的高效区域选择性和对映选择性单氢化。研究了底物范围并包括间位或对位上的未官能化和官能化取代基。具有取代基的底物如甲硅烷基保护的醇或缩酮以高区域选择性和高对映体过量（高达 98% ee）单氢化。
• Scalable Total Synthesis and Biological Evaluation of Haouamine A and Its Atropisomer
  作者：Noah Z. Burns、Irina N. Krylova、Rami N. Hannoush、Phil S. Baran

  DOI：10.1021/ja903745s

  日期：2009.7.8

  A total synthesis of the complex, bent aromatic ring-containing marine alkaloid haouamine A is achieved through a route in which every step (with the exception of the final deprotection) is performed on a gram-scale. This is accomplished through the development of a method for the dehydrogenation of cyclohexenones that allows for point-to-planar chirality transfer. This strategy makes it possible to program the desired atropisomeric outcome from a simple chiral cyclohexenone. By synthesizing atrop-haouamine A, this work has firmly established that natural haouamine exists as a single, nonequilibrating atropisomer. Finally, biological investigations demonstrate that the bent aromatic ring of this natural product is critical for anticancer activity against PC3 cells.