(-)-(4aR,4bR,8aR,10aR)-7,7-ethylenedioxy-2,4b,8,8,10a-pentamethyl-4a,4b,5,6,7,8,8a,9,10,10a-decahydrophenanthren-1(4H)-one | 874660-85-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (-)-(4aR,4bR,8aR,10aR)-7,7-ethylenedioxy-2,4b,8,8,10a-pentamethyl-4a,4b,5,6,7,8,8a,9,10,10a-decahydrophenanthren-1(4H)-one
• 英文别名: (4'aS,4'bR,8'aR,10'aR)-1',1',4'a,7',8'a-pentamethyl-4',4'a,4'b,5',8'a,9',10',10'a-octahydro-1'H-spiro[1,3-dioxolane-2,2'-phenanthrene]-8'(3'H)-one；(4'aR,4'bS,8'aR,10'aR)-2',4'b,8',8',10'a-pentamethylspiro[1,3-dioxolane-2,7'-4a,5,6,8a,9,10-hexahydro-4H-phenanthrene]-1'-one
• CAS: 874660-85-2
• 化学式: C₂₁H₃₂O₃
• 分子量: 332.483
• InChiKey: UORGOALJSZATRM-ACZWYYKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-(4aR,4bR,8aR,10aR)-7,7-ethylenedioxy-2,4b,8,8,10a-pentamethyl-4a,4b,5,6,7,8,8a,9,10,10a-decahydrophenanthren-1(4H)-one 在 乙酸酐 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.0h， 生成 (4'aR,4'bR,8'aR,10'aR)-1',1',4'a,7',8'a-pentamethyl-8'-methylidenespiro[1,3-dioxolane-2,2'-4,4b,5,9,10,10a-hexahydro-3H-phenanthrene]
  参考文献：
  名称：

  Enantiocontrolled Total Syntheses of Breviones A, B, and C

  摘要：

  Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an a-pyrone with a tricyclic diene prepared from an optically pure Wieland-Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization.

  DOI：

  10.1021/ja202874d
• 作为产物：
  描述：

  (+)-(4'aS,8'R,8'aR,10'aR)-(4'aβ,8'β,8'aβ,10'aα)-3',4',4'a,6',7',8',8'a,9',10',10'a-decahydro-8'-hydroxy-1',1',4'a,8'a-tetramethylspiro[1,3-dioxolane-2,2'(1'H)-phenanthrene] 在 六甲基磷酰三胺 、 5% Pd(II)/C(eggshell) 、 氢气 、 氧气 、 palladium diacetate 、 戴斯-马丁氧化剂 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 87.25h， 生成 (-)-(4aR,4bR,8aR,10aR)-7,7-ethylenedioxy-2,4b,8,8,10a-pentamethyl-4a,4b,5,6,7,8,8a,9,10,10a-decahydrophenanthren-1(4H)-one
  参考文献：
  名称：

  Enantiocontrolled Total Syntheses of Breviones A, B, and C

  摘要：

  Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an a-pyrone with a tricyclic diene prepared from an optically pure Wieland-Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization.

  DOI：

  10.1021/ja202874d

文献信息

• Synthesis and absolute configuration of brevione B, an allelochemical isolated from Penicillium sp.
  作者：Hirosato Takikawa、Yusuke Imamura、Mitsuru Sasaki

  DOI：10.1016/j.tet.2005.09.129

  日期：2006.1

  Breviones A–E (1–5), allelochemicals isolated from Penicillium brevicompactum Dierckx, are structurally unique diterpenoid derivatives. The first synthesis of both enantiomers of brevione B (2) was accomplished by employing the double SN2′-type tandem reaction as a key step, and the absolute configuration of the naturally occurring 2 was established.

  Breviones A-E（1 - 5）中，从分离的感物质短密青霉Dierckx，在结构上是独特的二萜类化合物的衍生物。brevione B（2）的两个对映异构体的第一次合成是通过使用双S N 2'型串联反应作为关键步骤完成的，并且确定了天然存在的2个对映体的绝对构型。
• Enantiocontrolled Total Syntheses of Breviones A, B, and C
  作者：Hiromasa Yokoe、Chika Mitsuhashi、Yoko Matsuoka、Tomoyuki Yoshimura、Masahiro Yoshida、Kozo Shishido

  DOI：10.1021/ja202874d

  日期：2011.6.15

  Enantiocontrolled total syntheses of the breviones A, B, and C have been accomplished using a highly diastereoselective oxidative coupling of an a-pyrone with a tricyclic diene prepared from an optically pure Wieland-Miescher ketone derivative through the 7-endo-trig mode of acyl radical cyclization.