(+)-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

• First Total Synthesis, Structure Revision, and Natural History of the Smallest Cytochalasin: (+)-Periconiasin G
  作者：Mehdi Zaghouani、Caroline Kunz、Laura Guédon、Florent Blanchard、Bastien Nay

  DOI：10.1002/chem.201603734

  日期：2016.10.17

  The total synthesis of the smallest cytochalasin isolated so far, periconiasin G, which bears a seven‐membered ring in lieu of the usual macrocycle, has been performed from both enantiomers of citronellal, relying on an intramolecular Diels–Alder reaction in favor of the natural endo stereochemistry. We show that, among the four synthesized stereoisomers, including the exo isomers, the one matching

  迄今为止分离出的最小的细胞松弛素的总合成，periconiasin G带有七元环而不是通常的大环，是由香茅醛的两个对映异构体进行的，依靠分子内的狄尔斯-阿尔德反应，有利于天然内立体化学。我们显示，在四种合成的立体异构体中，包括exo异构体，与天然产物的NMR数据相匹配的一种不是原始报告中指定的，对结构进行了修订。考虑到其天然历史，对以前从植物互生真菌中分离的天然产物进行了生物学研究，显示出对植物病原性真菌灰葡萄孢的显着效果 从而为防治这种有害生物开辟了新的机遇。
• 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：——