(+)-2-<(2R)-(2,6-Dimethyl)-5-heptenyl>-1,3-dioxolan | 1205-81-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧戊环
• 英文名称: (+)-2-<(2R)-(2,6-Dimethyl)-5-heptenyl>-1,3-dioxolan
• 英文别名: 2-((R)-2,6-dimethylhept-5-enyl)-1,3-dioxolane；(R)-7-[1,3]dioxolan-2-yl-2,6-dimethyl-hept-2-ene；(R)-7-[1,3]Dioxolan-2-yl-2,6-dimethyl-hept-2-en；2-[(2R)-2,6-dimethylhept-5-enyl]-1,3-dioxolane
• CAS: 1205-81-8
• 化学式: C₁₂H₂₂O₂
• 分子量: 198.305
• InChiKey: KCHXLUDCEMDEFL-LLVKDONJSA-N

物化性质

• 沸点：
  254.3±15.0 °C(predicted)
• 密度：
  0.910±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-2-<(2R)-(2,6-Dimethyl)-5-heptenyl>-1,3-dioxolan 在 镍 吡啶 、 盐酸 、 sodium hypochlorite 、 sodium tetrahydroborate 、 二甲基硫 、 硼酸三甲酯 、 盐酸羟胺 、 氢气 、 sodium acetate 、 臭氧 、 三氯氧磷 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 生成 (6R)-3,6-dimethyl-5,6,7,7a-tetrahydro-2(4H)-benzofuranone
  参考文献：
  名称：

  An efficient total synthesis of (−)-mintlactone and (+)-isomintlactone

  摘要：

  Total synthesis of (-)-mintlactone and (+)-isomintlactone has been achieved diastereoselectively via a fused butenolide construction strategy based on an intramolecular [3+2] cycloaddition reaction of nitrile oxide.

  DOI：

  10.1016/s0040-4039(00)61320-5
• 作为产物：
  描述：

  (+)-香茅醛 、 乙二醇 在 对甲苯磺酸 、 苯 作用下， 生成 (+)-2-<(2R)-(2,6-Dimethyl)-5-heptenyl>-1,3-dioxolan
  参考文献：
  名称：

  d-和l-异丁香菊酯及其相关化合物的合成

  摘要：

  从天然的d-香茅醛开始凝视，合成了d-铱和d-异艾罗霉素。1后者在氧化作用下提供了荆芥酸，其为荆芥内酯降解产物的对映体。两个样品的混合物提供了更高熔点的外消旋物。

  DOI：

  10.1016/0040-4020(59)80003-x

文献信息

• Synthesis of d- and l-isoiridomyrmecin and related compounds
  作者：K.J. Clark、G.I. Fray、R.H. Jaeger、Robert Robinson

  DOI：10.1016/0040-4020(59)80003-x

  日期：1959.1

  Staring from d-citronellal of natural origin, d-iridodial and d-isoiridomyrmecin were synthesised. 1 The latter furnished, on oxidation, a nepetalinic acid, which was the enantiomorph of a degradation product of nepetalactone. A mixture of the two specimens afforded a racemate of higher melting point.

  从天然的d-香茅醛开始凝视，合成了d-铱和d-异艾罗霉素。1后者在氧化作用下提供了荆芥酸，其为荆芥内酯降解产物的对映体。两个样品的混合物提供了更高熔点的外消旋物。
• First Asymmetric Total Syntheses of Cernuane-Type Lycopodium Alkaloids, Cernuine, and Cermizine D
  作者：Yasuhiro Nishikawa、Mariko Kitajima、Hiromitsu Takayama

  DOI：10.1021/ol800574v

  日期：2008.5.1

  The first total syntheses of two cernuane-type Lycopodium alkaloids, (-)-cernuine and (+)-cermizine D, were accomplished starting from (+)-citronellal. The syntheses involved organocatalytic alpha-amination to afford oxazolidinone, which is used for diastereoselective allylation, and asymmetric transfer aminoallylation followed by stereoselective construction of an aminal moiety as key steps.

  从（+）-香茅醛开始完成两种鹿尾草型石蒜碱生物碱（-）-鹿氨酸和（+）-cermizine D的第一个总合成。合成过程涉及有机催化的α-氨基化反应，以提供恶唑烷酮（用于非对映选择性烯丙基化）和不对称转移氨基烯丙基化，然后立体选择性地构建氨基部分，这是关键步骤。
• A divergent approach for the total syntheses of cernuane-type and quinolizidine-type Lycopodium alkaloids
  作者：Yasuhiro Nishikawa、Mariko Kitajima、Noriyuki Kogure、Hiromitsu Takayama

  DOI：10.1016/j.tet.2008.12.067

  日期：2009.2

  syntheses of cernuane-type and quinolizidine-type Lycopodium alkaloids are described. A common intermediate 5 for the two types of alkaloids was assembled practically from (+)-citronellal via organocatalytic α-amination, followed by the construction of oxazolidinone that was used for diastereoselective allylation. Key compound 5 was converted into cermizine C (3), and this in turn was converted into senepodine

  描述了天南星型和喹oli嗪型Lycopodium生物碱的不同总合成。两种生物碱的通用中间体5实际上是通过有机催化α-胺化反应从（+）香茅醛中组装而成的，然后构建了用于非对映选择性烯丙基化的恶唑烷酮。关键化合物5被转化为cermizine C（3），然后通过区域选择性Polonovsky-Potier反应又被转化为senepodine G（4）。代表性的鹿角烷型生物碱（-）-鹿氨酸（1）以及（+）-cermizine D（2）的总合成也由5完成 通过利用不对称转移氨基烯丙基化作为关键步骤。
• Acidic properties of sulfonic acid-functionalized FSM-16 mesoporous silica and its catalytic efficiency for acetalization of carbonyl compounds
  作者：K SHIMIZU、E HAYASHI、T HATAMACHI、T KODAMA、T HIGUCHI、A SATSUMA、Y KITAYAMA

  DOI：10.1016/j.jcat.2005.01.017

  日期：2005.4.1

  Propyl-sulfonic acid-functionalized FSM-16 mesoporous silica (SO3H-FSM) is prepared by a conventional post-modification method. For the acetalization of carbonyl compounds with ethylene glycol, SO3H-FSM shows a higher rate and 1,3-dioxolane yield than conventional heterogeneous solid acids such as zeolites, montmorillonite K10 clay, silica-alumina, and the sulfonic resin. SO3H-FSM is stable during the reaction, with no leaching and deactivation of sulfonic acid groups, and is reusable without loss of its activity. The acidity and hydrophilicity of SO3H-FSM are well characterized by the microcalorimetry of NH3 adsorption, NH3-TPD, and H2O-TPD, and the result is compared with those for various aluminosilicate zeolites (HZSM5, HBEA, HY) and K10 clay. It is found that NH3-TPD is not suitable for characterizing the acidity of SO3H-FSM, because the decomposition of SO3H groups on SO3H-FSM begins above 200 degrees C. An NH3 adsorption microcalorimetric experiment at 150 degrees C shows that, compared with HZSM5, SO3H-FSM has a smaller number of acid sites but has a similar number of strong acid sites with ammonia adsorption heat above 140 kJ mol(-1). Comparison of the structural properties and catalytic results shows that a large pore diameter and low hydrophilicity are required to obtain high activity. Bronsted acid sites with a relatively strong acid strength are more suitable for this reaction, but the high acid concentration is not indispensable. The high activity of SO3H-FSM should be caused by the presence of the strong Bronsted acid sites in the mesopore with a relatively low hydrophilicity, where both reactants can smoothly access the acid sites. (c) 2005 Elsevier Inc. All rights reserved.
• Kuhnke, Joachim; Bohlmann, Ferdinand, Liebigs Annalen der Chemie, 1988, p. 743 - 748
  作者：Kuhnke, Joachim、Bohlmann, Ferdinand

  DOI：——

  日期：——