(+/-)-exo-dehydro-2-desoxystemodinone | 929635-55-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (+/-)-exo-dehydro-2-desoxystemodinone
• 英文别名: Stemod-13(17)-ene；(1R,2S,7S,10S,12S)-2,6,6-trimethyl-13-methylidenetetracyclo[10.3.1.01,10.02,7]hexadecane
• CAS: 929635-55-2
• 化学式: C₂₀H₃₂
• 分子量: 272.474
• InChiKey: GNNRCBBKCVNPSC-VDWQKOAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  rac-(1R,4a'R,8a'R)-4,5',5',8a'-tetramethyl-3',4',4a',5',6',7',8',8a'-octahydro-2'H-spiro[cyclohexane-1,1'-naphthalen]-3-en-2'-one 在 氢氧化钾 、 samarium diiodide 、 草酰氯 、 sodium 、 二甲基氯化铝 、 二甲基亚砜 、 三乙胺 、 肼 、 叔丁醇 作用下， 以 四氢呋喃 、 二氯甲烷 、 氨 、 二乙二醇 为溶剂， 反应 35.02h， 生成 (+/-)-exo-dehydro-2-desoxystemodinone
  参考文献：
  名称：

  Total synthesis of (.+-.)-2-desoxystemodinone. A novel hydroxyl-assisted, intramolecular ene reaction

  摘要：

  DOI：

  10.1021/ja00248a065

文献信息

• Identification of syn-stemodene synthase
  申请人：Iowa State University Research Foundation, Inc.

  公开号：US07833748B1

  公开（公告）日：2010-11-16

  The present invention relates to the isolation, purification, sequencing, and functional characterization of the class I diterpene synthase sequence OsKSL11. Transcriptional control of OsKSL11 provides a means of regulating production of stemodene. Further, since OsKSL11 is highly homologous to OsKSL8, identification of the sequence of OsKSL11 will facilitate identification of underlying enzymatic determinants that affect product outcomes with these enzymes.

  本发明涉及到类I二萜合酶序列OsKSL11的分离、纯化、测序和功能表征。OsKSL11的转录控制提供了调节stemodene产量的手段。此外，由于OsKSL11与OsKSL8高度同源，因此确定OsKSL11序列将有助于确定影响这些酶产物结果的基础酶确定因素。
• Total synthesis of (.+-.)-2-desoxystemodinone. A novel hydroxyl-assisted, intramolecular ene reaction
  作者：James D. White、Todd C. Somers

  DOI：10.1021/ja00248a065

  日期：1987.7
• An unexpected diterpene cyclase from rice: Functional identification of a stemodene synthase
  作者：Dana Morrone、Yinghua Jin、Meimei Xu、Suh-Yeon Choi、Robert M. Coates、Reuben J. Peters

  DOI：10.1016/j.abb.2005.09.001

  日期：2006.4

  We have cloned a novel diterpene synthase (OsKSL11) from rice that produces stemod-13(17)-ene from syn-copalyl diphosphate. Notably, this gene sequence was not predicted from the extensive sequence information available for rice. nor, despite extensive phytochemical investigations, has this diterpene or any derived natural product previously been reported in rice plants. OsKSL11 represents the first identified stemodene synthase, which catalyzes the committed step in biosynthesis of the stemodane family of diterpenoid natural products, some of which possess antiviral activity. In addition, OsKSL11 is highly homologous to the mechanistically similar stemarene synthase recently identified front rice, making this pair of diterpene cyclases an excellent model system for investigating the enzymatic determinants for differential product outcome. The unexpected nature of this cyclase and its product parallels recent observations of preplant previously unrecognized natural products metabolism in Arabidopsis thaliana, suggesting that many, if not all, plant species will prove to have extensive biosynthetic capacity. (c) 2005 Elsevier Inc. All rights reserved.
• Construction of the Stemodane Nucleus by a Hydroxyl-Directed Intramolecular Ene Reaction. Total Synthesis of (.+-.)-2-Desoxystemodinone
  作者：James D. White、Todd C. Somers

  DOI：10.1021/ja00101a012

  日期：1994.11

  A synthesis of the diterpene 2-desoxystemodinone was completed from the known tricyclic ketone 9 in eight steps and 35% overall yield. The key step involved a thermal intramolecular ene reaction of alpha-hydroxy aldehyde 21 which led to 24 in 94% yield. By contrast, a Lewis acid-catalyzed ene reaction of 21 gave oxetane 25 as the major product. The pivotal role of the hydroxyl substituent of 21 in facilitating the ene reaction was demonstrated and is rationalized by a hydrogen bond which orients the carbonyl in a favorable conformation for rearrangement.