(2R^*,5S^*)-2-methyl-1,6-dioxaspiro<4,5>decane | 68108-91-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R^*,5S^*)-2-methyl-1,6-dioxaspiro<4,5>decane
• 英文别名: (-)-2S,5RS-methyl-1.6-dioxa-spiro<4.5>decane；trans-2-methyl-1,6-dioxaspiro<4.5>decane；(E)-2-methyl-1,6-dioxaspiro<4.5>decanes；(E)-2-methyl-1,6-dioxaspiro<4.5>decane；E-methyl-1,6-dioxaspiro<4.5>decane；(2R,5S)-2-methyl-1,10-dioxaspiro[4.5]decane
• CAS: 68108-91-8；68108-92-9；73046-14-7；73137-64-1；73137-65-2；76042-02-9；76042-03-0；76119-64-7；76119-65-8
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: JQEFEBJVAHPKHX-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,6-dioxaspiro[4.5]decan-2-one 在 palladium-barium carbonate 氢气 作用下， 生成 (2R^*,5S^*)-2-methyl-1,6-dioxaspiro<4,5>decane
  参考文献：
  名称：

  A novel method for the synthesis of spiroketal systems. Synthesis of the pheromones of the common wasp and the olive fruit fly

  摘要：

  Total syntheses of the pheromones of the common wasp and the olive fruit fly were accomplished by a strategy in which the key transformation involved the cleavage of tetrahydrofuran with (tert-butyldimethyl-sily)manganese pentacarbonyl followed by sequential insertion of ethyl acrylate.

  DOI：

  10.1021/jo00010a005

文献信息

• Synthesis of Spiroacetal Pheromones via Metalated Hydrazones
  作者：Dieter Enders、Walter Dahmen、Eleonore Dederichs、Winfried Gatzweiler、Peter Weuster

  DOI：10.1055/s-1990-27080

  日期：——

  The synthesis of simple alkyl substituted spiroacetals by α,α′-alkylation of metalated acetone dimethylhydrazone with appropriate electrophiles and subsequent acid catalyzed cleavage and ring closure of the products is described.

  通过合适的亲电试剂与金属化丙酮二甲基脲的α,α′-烷基化反应，随后进行酸催化的断裂和环化闭合，描述了简单烷基取代螺缩醛的合成方法。
• Synthesis of optically active 2s-, and 7s-methyl-1.6-dioxa-spiro[4.5] decane, the pheromone components of Paravespula vulgaris (L.), from S-ethyl lactate.
  作者：K. Hintzer、R. Weber、V. Schurig

  DOI：10.1016/0040-4039(81)80039-1

  日期：1981.1

  (−)-2S, 5RS-1 and (−]-7S, 5S-2 are obtained from S-ethyl lactate 4 and their absolute configuration is thus directly correlated. Accurate enantiomeric compositions of intermediates and products were measured by complexation gas chromatography on nickel-, and manganese-bis-3-heptafluorobutyryl-1R-camphorate, 3. It could be conclusively established that the syntheses proceed with a high degree of preservation

  （-）-2S，5RS-1和（-]-7S，5S-2是由乳酸S-乙酯4得到的，因此它们的绝对构型直接相关，中间体和产物的精确对映体组成通过络合气相色谱法测定。镍-和锰-双-3-3七氟丁酰-1R-樟脑膦酸酯3.可以确定地确定合成过程在高度保留构型的情况下进行。
• Diastereoselective route to (2R,5S)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane, a pheromone component of the wasp Paravespula vulgaris
  作者：Paulo H.G. Zarbin、Alfredo R.M. de Oliveira、Carlos E. Delay

  DOI：10.1016/s0040-4039(03)01716-7

  日期：2003.9

  A diastereoselective approach to (2R,5S)- and (2S,5S)-2-methyl-1,6-dioxaspiro[4.5]decane 1 and 1a is described. The route starts with an alkylation reaction among the cyclopentanone N,N-dimethylhydrazone 6 and the chiral iodides (R)-3 or (S)-3, derived from the enantiomers of ethyl β-hydroxybutyrate, controlling the estereocenter at C-2 of the molecules. The alkylated products 7 and 7a were easily

  描述了对（2 R，5 S）-和（2 S，5 S）-2-甲基-1,6-二氧杂螺[4.5]癸烷1和1a的非对映选择性方法。该路线以环戊酮N，N-二甲基hydr 6与手性碘化物（R）-3或（S）-3之间的烷基化反应开始，该碘化物来自β-羟基丁酸乙酯的对映异构体，控制酯中心在C-2处。分子。烷基化产物7和7a容易转化为1,8- O-TBS-1,8-二羟基-5-壬酸9和9a分四个步骤，随后在酸性介质中进行立体选择性螺酮缩合，得到化合物1和1a的Z：E混合物（1：2）。
• Synthetic studies on spiroketal natural products. III. Enantioselective synthesis of 1,6-dioxaspiro(4.5)decane compounds.
  作者：CHUZO IWATA、YASUNORI MORITANI、KENJI SUGIYAMA、HITOSHI IZAKI、TOSHIO KUROKI、TAKESHI IMANISHI

  DOI：10.1248/cpb.36.4785

  日期：——

  Two enantiomers of 1, 6-dioxaspiro [4.5] decane (1) and all four stereoisomers of 2-methyl-1, 6-dioxaspiro [4.5] decane (an insect pheromone)(9) were successfully synthesized via a crucial step, an asymmetric five-membered ring cyclization induced by a sulfinyl chirality. The alcohol (6), prepared from the optically active sulfoxide (2), was treated with potassium hydride to give the spiroketal (7), which was transformed into the isomer (8) by acid. Reductive desulfurization of these products furnished R-1 and S-1, respectively. The ketone (10), also prepared from 2, was reduced with diisobutylaluminum hydride (DIBAL) or DIBAL-ZnCl2 to afford selectively 15a or 15b, respectively. Base-catalyzedicyclization gave 21a and 21b, which were convertible to 22a and 22b under acidic conditions. The four isomers (21a, 21b, 22a, and 22b) were efficiently transformed into 9a, 9b, 9c, and 9d by removal of the chiral auxiliary.

  成功合成了1, 6-二氧杂螺[4.5]十烷（1）的两个对映体以及2-甲基-1, 6-二氧杂螺[4.5]十烷（昆虫信息素）（9）的所有四个立体异构体，关键步骤是一种由硫酰手性诱导的不对称五元环环化反应。由光学活性的硫氧化物（2）制备的醇（6），与氢化钾反应生成螺酮（7），该物质在酸的作用下转化为异构体（8）。这些化合物的还原脱硫反应分别生成R-1和S-1。酮（10），同样由2制备，经过二异丁基铝氢化物（DIBAL）或DIBAL-ZnCl2还原，分别选择性地得到15a或15b。碱催化的环化反应生成21a和21b，在酸性条件下可以转化为22a和22b。通过去除手性辅佐基，这四个异构体（21a、21b、22a和22b）有效地转化为9a、9b、9c和9d。
• A new and facile route to spiro-ketal skeleton highly stereoselective CO bond formation by intramolecular Michael addition to δ,β-unsaturated sulfoxides
  作者：Chuzo Iwata、Kohji Hattori、Shuji Uchida、Takeshi Imanishi

  DOI：10.1016/s0040-4039(01)81347-2

  日期：1984.1

  Diastereoisomerically pure (E)-and (Z)-2-methyl-1,6-dioxaspiro [4.5]-decane (insect pheromone) was efficiently prepared via a highly stereo controlled intramolecular Michael addition of hydroxyl group to an unsaturated sulfoxide moiety during the crucial cyclization step.

  非立体异构的纯（E）和（Z）-2-甲基-1,6-二氧杂螺[4.5]-癸烷（昆虫信息素）是通过在反应过程中高度立体控制的分子内迈克尔将羟基加成到不饱和亚砜部分而有效地制备的。至关重要的环化步骤。