(1R,4R,5S)-1,8-dimethyl-4-(1'-methylethenyl)spiro[4.5]dec-7-ene | 213020-40-7

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (1R,4R,5S)-1,8-dimethyl-4-(1'-methylethenyl)spiro[4.5]dec-7-ene
• 英文别名: α-neocallitropsene；(1R,4R,5S)-(+)-acoradiene；4-epi-α-acoradiene；(+)-acoradiene；(1R,4R,5S)-1,8-Dimethyl-4-(prop-1-en-2-yl)spiro[4.5]dec-7-ene；(1R,4R,5S)-1,8-dimethyl-4-prop-1-en-2-ylspiro[4.5]dec-8-ene
• CAS: 213020-40-7
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: DVBSKQAFCDJNSL-RBSFLKMASA-N

物化性质

• 沸点：
  273.1±20.0 °C(Predicted)
• 密度：
  0.89±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1R,4R,5S)-1,8-dimethyl-4-(1'-methylethenyl)spiro[4.5]dec-7-ene 在 lithium 、 乙胺 作用下， 以100%的产率得到rac-(1R,4R,5S)-1-isopropyl-4,8-dimethylspiro<4.5>dec-7-ene
  参考文献：
  名称：

  新型的环戊达[ c ]苯并呋喃中间体，用于合成cor烷-卢卡素倍半萜烯：（±）-β-二十碳烯醇和（±）-二十碳烯酮的全合成

  摘要：

  由螺二烯酮酯（6a）和（6b）合成环戊[ c ]苯并呋喃衍生物（5a）和（5b ）。分别; 并通过将它们转化为（±）-β-acoreno（4a）和（±）和（±）-acorenone（1）来说明这些中间体在天竺葵-ska草香倍半萜合成中的用途。

  DOI：

  10.1039/c39840000781
• 作为产物：
  描述：

  cis-cis-Puleganolid 在 Grubbs catalyst first generation 正丁基锂 、 双[Α,Α-双(三氟甲基)苯甲醇合]二苯硫 、 四甲基乙二胺 、 四丁基氟化铵 、 lithium 、 二异丁基氢化铝 、 乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 吡啶 、 乙二醇二甲醚 、 正己烷 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 76.0h， 生成 (1R,4R,5S)-1,8-dimethyl-4-(1'-methylethenyl)spiro[4.5]dec-7-ene
  参考文献：
  名称：

  Kurosawa, Satoshi; Bando, Masahiko; Mori, Kenji, European Journal of Organic Chemistry, 2001, # 23, p. 4395 - 4399

  摘要：

  DOI：

文献信息

• Bisabolyl-Derived Sesquiterpenes from Tobacco 5-Epi-aristolochene Synthase-Catalyzed Cyclization of (2<i>Z</i>,6<i>E</i>)-Farnesyl Diphosphate
  作者：Juan A. Faraldos、Paul E. O’Maille、Nikki Dellas、Joseph P. Noel、Robert M. Coates

  DOI：10.1021/ja909886q

  日期：2010.3.31

  acyclic allylic alcohols (2Z,6E)-farnesol (6.7%) and nerolidol (3.6%), five cyclic sesquiterpene hydrocarbons and two cyclic sesquiterpene alcohols: (+)-2-epi-prezizaene (44%), (-)-alpha-cedrene (21.5%), (R)-(-)-beta-curcumene (15.5%), alpha-acoradiene (3.9%), 4-epi-alpha-acoradiene (1.3%), and equal amounts of alpha-bisabolol (1.8%) and epi-alpha-bisalolol (1.8%). The structures, stereochemistry, and

  我们报告了由烟草 5-epi-马兜铃烯合酶 (TEAS) 有效催化的前所未有的 1,6-环化（cisoid 途径）产生的七种红没药酰基衍生倍半萜的结构和立体化学。使用 (2Z,6E)-法呢基二磷酸作为重组 TEAS 的替代底物导致强烈的酶促环化作用，生成一系列完全 (>/=99.5%) 来自 cisoid 途径的产物，而这些相同的产物占约. 使用 (2E,6E)-法呢基二磷酸获得的总烃的 2.5%。除了无环烯丙醇 (2Z,6E)-法呢醇 (6.7%) 和橙花醇 (3.6%)、五种环状倍半萜烃和两种环状倍半萜醇外，对 2Z,6E 底物的制备培养提取物进行色谱分离： (+)-2-epi-prezizaene (44%), (-)-α-雪松烯 (21.5%)、(R)-(-)-β-姜黄烯 (15.5%)、α-acoradiene (3.9%)、4-epi-alpha-acoradiene (1.3%)
• Structural Elucidation of Cisoid and Transoid Cyclization Pathways of a Sesquiterpene Synthase Using 2-Fluorofarnesyl Diphosphates
  作者：Joseph P. Noel、Nikki Dellas、Juan A. Faraldos、Marylin Zhao、B. Andes Hess、Lidia Smentek、Robert M. Coates、Paul E. O’Maille

  DOI：10.1021/cb900295g

  日期：2010.4.16

  Sesquiterpene skeletal complexity in nature originates from the enzyme catalyzed ionization of (trans,trans)-farnesyl diphosphate (FPP) (1a) and subsequent cyclization along either 2,3-transold or 2,3-cisoid farnesyl cation pathways. Tobacco 5-epi-aristolochene synthase (TEAS), a transoid synthase, produces cisoid products as a component of its minor product spectrum. To investigate the cryptic cisoid cyclization pathway in TEAS, we employed (cis,trans)-FPP (1b) as an alternative substrate. Strikingly, TEAS was catalytically robust in the enzymatic conversion of (cis,trans)-FPP (1b) to exclusively (>= 99.5%) cisoid products. Further, crystallographic characterization of wild-type TEAS and a catalytically promiscuous mutant (M4 TEAS) with 2-fluoro analogues of both all-trans FPP (1a) and (cis,trans)-FPP (1b) revealed binding modes consistent with preorganization of the farnesyl chain These results provide a structural glimpse into both cisoid and transoid,cyclization pathways efficiently templated by a single enzyme active site, consistent with the recently elucidated stereochemistry of the cisoid products. Further, computational studies using density functional theory calculations reveal concerted highly asynchronous cyclization pathways leading to the major cisoid cyclization products. The implications of these discoveries for expanded sesquiterpene diversity in nature are discussed.
• Iwata, Chuzo; Fusaka, Takafumi; Maezaki, Naoyoshi, Chemical and pharmaceutical bulletin, <hi>1988</hi>, vol. 36, # 5, p. 1638 - 1645
  作者：Iwata, Chuzo、Fusaka, Takafumi、Maezaki, Naoyoshi、Nakamura, Shizou、Shinoo, Yasutaka、et al.

  DOI：——

  日期：——
• Kurosawa, Satoshi; Bando, Masahiko; Mori, Kenji, European Journal of Organic Chemistry, 2001, # 23, p. 4395 - 4399
  作者：Kurosawa, Satoshi、Bando, Masahiko、Mori, Kenji

  DOI：——

  日期：——
• Novel cyclopenta[c]benzofuran intermediates for the synthesis of acorane–alskane sesquiterpenes: total synthesis of (±)-β-acorenol and (±)-acorenone
  作者：Chuzo Iwata、Shizuo Nakamura、Yasutaka Shinoo、Takafumi Fusaka、Michie Kishimoto、Hidekazu Uetsuji、Naoyoshi Maezaki、Tetsuaki Tanaka

  DOI：10.1039/c39840000781

  日期：——

  Cyclopenta[c]benzofuran derivatives (5a) and (5b) were synthesized from spirodienone esters (6a) and (6b). respectively; and the utility of these intermediates in acorane-alaskane sesquiterpene synthesis is illustrated by their conversion into(±)-β-acoreno (4a) and (±) and (±)-acorenone (1).

  由螺二烯酮酯（6a）和（6b）合成环戊[ c ]苯并呋喃衍生物（5a）和（5b ）。分别; 并通过将它们转化为（±）-β-acoreno（4a）和（±）和（±）-acorenone（1）来说明这些中间体在天竺葵-ska草香倍半萜合成中的用途。