(4S,5S,9R,10R,1'R,5'R)-methyl 8-bromo-4-t-butyldiphenylsilyloxy-1,7-dioxo-9-{2''-[5'-(3-furyl)-1'-methyl-2'-oxocyclopent-1'-yl]-eth-1''-yl}-decahydronaphthalene-10-carboxylate | 448961-06-6

• 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: (4S,5S,9R,10R,1'R,5'R)-methyl 8-bromo-4-t-butyldiphenylsilyloxy-1,7-dioxo-9-{2''-[5'-(3-furyl)-1'-methyl-2'-oxocyclopent-1'-yl]-eth-1''-yl}-decahydronaphthalene-10-carboxylate
• 英文别名: methyl (1S,4aR,5R,8aS)-6-bromo-1-[tert-butyl(diphenyl)silyl]oxy-5-[2-[(1R,2R)-2-(furan-3-yl)-1-methyl-5-oxocyclopentyl]ethyl]-4,7-dioxo-2,3,5,6,8,8a-hexahydro-1H-naphthalene-4a-carboxylate
• CAS: 448961-06-6
• 化学式: C₄₀H₄₇BrO₇Si
• 分子量: 747.798
• InChiKey: DGFJTTAANXVQBD-BVXPTSHESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.95
• 重原子数：
  49
• 可旋转键数：
  11
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  99.9
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (4S,5S,9R,10R,1'R,5'R)-methyl 8-bromo-4-t-butyldiphenylsilyloxy-1,7-dioxo-9-{2''-[5'-(3-furyl)-1'-methyl-2'-oxocyclopent-1'-yl]-eth-1''-yl}-decahydronaphthalene-10-carboxylate 在 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以78%的产率得到(4S,5S,9S,10S,1'R,5'R)-methyl 4-t-butyldiphenylsilyloxy-1,7-dioxo-9-{2''-[5'-(3-furyl)-1'-methyl-2'-oxo-cylopent-1'-yl]-eth-1''-yl}-decahydronaphthalene-10-carboxylate
  参考文献：
  名称：

  A Convergent Synthesis of the Cardenolide Skeleton:  Intramolecular Aldol Condensation via Reduction of α-Bromoketones

  摘要：

  Synthesis of the highly biologically valuable cardenolide backbone was achieved via anionic polycyclization. Bromoketone 18, obtained from double-Michael cycloaddition between cyclohexenone 14 and gamma,delta-unsaturated beta-ketoester 16, was efficiently aldolized under reductive conditions. The highly functionalized tetracyclic compound 52 is an important synthetic intermediate that is potentially amenable to natural cardenolide total synthesis.

  DOI：

  10.1021/jo025612b
• 作为产物：
  描述：

  (4S)-4-t-butyldiphenylsilyloxy-2-carbomethoxycyclohex-2-en-1-one 在 caesium carbonate 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 (4S,5S,9R,10R,1'R,5'R)-methyl 8-bromo-4-t-butyldiphenylsilyloxy-1,7-dioxo-9-{2''-[5'-(3-furyl)-1'-methyl-2'-oxocyclopent-1'-yl]-eth-1''-yl}-decahydronaphthalene-10-carboxylate
  参考文献：
  名称：

  旨在通过阴离子多环化反应合成不对称的心脏活性类固醇的研究。

  摘要：

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。

  DOI：

  10.1021/ol027125o

文献信息

• A Convergent Synthesis of the Cardenolide Skeleton:  Intramolecular Aldol Condensation via Reduction of α-Bromoketones
  作者：Daniel Chapdelaine、Julie Belzile、Pierre Deslongchamps

  DOI：10.1021/jo025612b

  日期：2002.8.1

  Synthesis of the highly biologically valuable cardenolide backbone was achieved via anionic polycyclization. Bromoketone 18, obtained from double-Michael cycloaddition between cyclohexenone 14 and gamma,delta-unsaturated beta-ketoester 16, was efficiently aldolized under reductive conditions. The highly functionalized tetracyclic compound 52 is an important synthetic intermediate that is potentially amenable to natural cardenolide total synthesis.
• Studies Directed toward Asymmetric Synthesis of Cardioactive Steroids via Anionic Polycyclization
  作者：Zhixiang Yang、Dean Shannon、Vouy-Linh Truong、Pierre Deslongchamps

  DOI：10.1021/ol027125o

  日期：2002.12.1

  [reaction: see text] The use of anionic polycyclization (AP) in constructing the steroidal backbone of cardenolides was investigated. The reaction of 2-carbomethoxy-2-cyclohexenone I with the enolate of Nazarov reagent II gave, after decarboxylation and aldol condensation, steroid III with control of stereochemistry.

  [反应：见正文]研究了阴离子多环化（AP）在构建烯醇内酯类固醇骨架中的应用。2-羧甲氧基-2-环己烯酮Ⅰ与纳扎罗夫试剂Ⅱ的烯醇化物反应，在脱羧和醛醇缩合后，在立体化学控制下得到甾族化合物Ⅲ。