(-)-(1R,3R,4aS,8aS)-decahydro-5,5,8a-trimethyl-3-tert-butyldimethylsiloxy-2-methylene-1-naphthaleneacetaldehyde | 577968-47-9

• 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: (-)-(1R,3R,4aS,8aS)-decahydro-5,5,8a-trimethyl-3-tert-butyldimethylsiloxy-2-methylene-1-naphthaleneacetaldehyde
• 英文别名: 2-[(1R,3S,4aS,8aS)-3-[tert-butyl(dimethyl)silyl]oxy-5,5,8a-trimethyl-2-methylidene-3,4,4a,6,7,8-hexahydro-1H-naphthalen-1-yl]acetaldehyde
• CAS: 577968-47-9
• 化学式: C₂₂H₄₀O₂Si
• 分子量: 364.644
• InChiKey: VLJLRDZDYAQWDV-ZVVDCOBXSA-N

物化性质

• 沸点：
  396.0±25.0 °C(predicted)
• 密度：
  0.93±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.37
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  (2-氧代四氢呋喃-3-基)膦酸二乙酯 、 (-)-(1R,3R,4aS,8aS)-decahydro-5,5,8a-trimethyl-3-tert-butyldimethylsiloxy-2-methylene-1-naphthaleneacetaldehyde 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 1.0h， 以63%的产率得到(3E)-3-[2-[(1R,3S,4aS,8aS)-3-[tert-butyl(dimethyl)silyl]oxy-5,5,8a-trimethyl-2-methylidene-3,4,4a,6,7,8-hexahydro-1H-naphthalen-1-yl]ethylidene]oxolan-2-one
  参考文献：
  名称：

  Concise Syntheses of Coronarin A, Coronarin E, Austrochaparol and Pacovatinin A

  摘要：

  从合成产物(+)-albicanyl acetate (6)中获得了(+)-coronarin A (1)、(+)-coronarin E (2)、(+)-austrochaparol (3)和(+)-pacovatinin A (4)的完全合成。(+)-albicanol (5)的Dess-Martin氧化反应来自化学酶产物(6)，生成醛(7)，后者与β-呋喃甲基杂芳砜(8或9)进行Julia一锅法烯化反应，得到具有高顺式选择性的(+)-反式coronarin E (2)和(+)-顺式coronarin E (12)。从(+)-反式coronarin E (2)中获得了(+)-coronarin A (1)的合成，而(+)-顺式coronarin E (12)则转化为天然产物(+)-(5S,9S,10S)-15,16-epoxy-8(17),13(16),14-labdatriene (13)和(+)-austrochaparol (3)。通过(+)-3的不对称合成，确定(+)-3的绝对结构为5S,7R,9R,10S构型。(+)-albicanol (5)的同分异构化反应后，发生烯丙基氧化反应，生成(7α)-

  DOI：

  10.1248/cpb.56.398
• 作为产物：
  描述：

  香紫苏内酯 在 2,3,5-三甲基吡啶 、 甲醇 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 sodium carbonate 、 silver nitrate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 55.0h， 生成 (-)-(1R,3R,4aS,8aS)-decahydro-5,5,8a-trimethyl-3-tert-butyldimethylsiloxy-2-methylene-1-naphthaleneacetaldehyde
  参考文献：
  名称：

  A study on the synthesis of antiangiogenic (+)-coronarin A and congeners from (+)-sclareolide

  摘要：

  Coronarin A 1, epi-coronarin A 2 and some synthetic intermediates 14a and 14b synthesized from sclareolide exhibit good growth inhibition activities on HUVEC proliferation. In particular, coronarin A 1 and epi-coronarin A 2 effectively suppressed the growth factor induced tube formation of HUVEC at the concentration of 10 mug/mL. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(03)00345-7

文献信息

• Concise Syntheses of Coronarin A, Coronarin E, Austrochaparol and Pacovatinin A
  作者：Takahiro Miyake、Keisuke Uda、Masako Kinoshita、Mikio Fujii、Hiroyuki Akita

  DOI：10.1248/cpb.56.398

  日期：——

  Total syntheses of (+)-coronarin A (1), (+)-coronarin E (2), (+)-austrochaparol (3) and (+)-pacovatinin A (4) were achieved from the synthetic (+)-albicanyl acetate (6). Dess–Martin oxidation of (+)-albicanol (5) derived from the chemoenzymatic product (6) gave an aldehyde (7), which was subjected to Julia one-pot olefination using β-furylmethyl-heteroaromatic sulfones (8 or 9 ) gave (+)-trans coronarin E (2) and (+)-cis coronarin E (12) with high cis-selectivity. The synthesis of (+)-coronarin A (1) from (+)-trans coronarin E (2) was achiev-ed, while (+)-cis coronarin E (12) was converted to the natural products (+)-(5S,9S,10S)-15,16-epoxy-8(17),13(16),14-labdatriene (13) and (+)-austrochaparol (3). By the asymmetric synthesis of (+)-3, the absolute structure of (+)-3 was determined to be 5S, 7R, 9R, 10S configurations. Homologation of (+)-albicanol (5) followed by allylic oxidation gave (7α)-hydroxy nitrile (17), which was finally converted to the natural (+)-pacovatinin A (4) in 8 steps from (+)-albicanol (5).

  从合成产物(+)-albicanyl acetate (6)中获得了(+)-coronarin A (1)、(+)-coronarin E (2)、(+)-austrochaparol (3)和(+)-pacovatinin A (4)的完全合成。(+)-albicanol (5)的Dess-Martin氧化反应来自化学酶产物(6)，生成醛(7)，后者与β-呋喃甲基杂芳砜(8或9)进行Julia一锅法烯化反应，得到具有高顺式选择性的(+)-反式coronarin E (2)和(+)-顺式coronarin E (12)。从(+)-反式coronarin E (2)中获得了(+)-coronarin A (1)的合成，而(+)-顺式coronarin E (12)则转化为天然产物(+)-(5S,9S,10S)-15,16-epoxy-8(17),13(16),14-labdatriene (13)和(+)-austrochaparol (3)。通过(+)-3的不对称合成，确定(+)-3的绝对结构为5S,7R,9R,10S构型。(+)-albicanol (5)的同分异构化反应后，发生烯丙基氧化反应，生成(7α)-
• A study on the synthesis of antiangiogenic (+)-coronarin A and congeners from (+)-sclareolide
  作者：Sangtae Oh、In Howa Jeong、Woon-Seob Shin、Seokjoon Lee

  DOI：10.1016/s0960-894x(03)00345-7

  日期：2003.6

  Coronarin A 1, epi-coronarin A 2 and some synthetic intermediates 14a and 14b synthesized from sclareolide exhibit good growth inhibition activities on HUVEC proliferation. In particular, coronarin A 1 and epi-coronarin A 2 effectively suppressed the growth factor induced tube formation of HUVEC at the concentration of 10 mug/mL. (C) 2003 Elsevier Science Ltd. All rights reserved.