4-(1-甲基乙基)-环己-2-烯-1-酮 | 100295-52-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 4-(1-甲基乙基)-环己-2-烯-1-酮
• 英文名称: (S)-(+)-Cryptone
• 英文别名: 4-isopropyl-2-cyclohexen-1-one；4-Isopropyl-2-cyclohexen-1-one, (S)-(+)-；(4S)-4-propan-2-ylcyclohex-2-en-1-one
• CAS: 100295-52-1
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: AANMVENRNJYEMK-QMMMGPOBSA-N

物化性质

• 沸点：
  208.5±10.0 °C(Predicted)
• 密度：
  0.931±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(1-甲基乙基)-环己-2-烯-1-酮 在 18-冠醚-6 、 potassium hydride 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 、 苯 为溶剂， 反应 20.42h， 生成 (4S,5E)-7-亚甲基-4-(1-甲基乙基)-5-环癸烯-1-酮
  参考文献：
  名称：

  Cyclobutene bridgehead olefin route to the American cockroach sex pheromone, periplanone-B

  摘要：

  DOI：

  10.1021/ja00326a028
• 作为产物：
  描述：

  4-异丙基环己-2-烯-1-酮 在 chromium(VI) oxide 、 Candida antarctica lipase B 、 sodium tetrahydroborate 、 cerium(III) chloride 、 硫酸 作用下， 以 甲醇 、 二氯甲烷 、 异丙醚 、 丙酮 为溶剂， 反应 5.17h， 生成 4-(1-甲基乙基)-环己-2-烯-1-酮
  参考文献：
  名称：

  Enantiomerically enriched cryptone by lipase catalysed kinetic resolution

  摘要：

  Thiophenol was added to racemic cryptone (4-isopropyl-2-cyclohexene-1-one) and the resulting 1,4-addition products, cis- and trans-4-isopropyl-3-(phenyisulfanyl)cyclohexanone were separated and the latter reduced to rac-1,3-cis-1,4-trans-4-isopropyl3-(phenylsulfanyl)cyclohexanol, which was subjected to lipase catalysed resolution by acylation catalysed by CAL-B (Candida antarctica lipase B). The alcohol enantiorners obtained were oxidised. The remaining alcohol was separated from the produced acetate, which was hydrolysed to the alcohol. The initial products, probably sulfoxidoketones spontaneously decomposed to furnish enantiomerically enriched (R)- and (S)-cryptone with up to 76% and 98% ee, respectively. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.12.012

文献信息

• Synthesis of (−)-Piperitylmagnolol Featuring <i>ortho</i>-Selective Deiodination and Pd-Catalyzed Allylation
  作者：Atsushi Ikoma、Narihito Ogawa、Daiki Kondo、Hiroki Kawada、Yuichi Kobayashi

  DOI：10.1021/acs.orglett.6b00706

  日期：2016.5.6

  A 1,4-addition strategy using an enone and a copper reagent was studied for the synthesis of (−)-piperitylmagnolol. A MOM-protected biphenol copper reagent was added to BF3·OEt2-activated 4-isopropylcyclohexenone, whereas 1,4-addition of protected monophenol reagents possessing an allyl group was found to be unsuccessful. The allyl group was later attached to the p-,p′-diiodo-biphenol ring by Pd-catalyzed

  研究了使用烯酮和铜试剂的1，4-加成策略，用于合成（-）-哌啶基厚朴酚。将MOM保护的双酚铜试剂添加到BF 3 ·OEt 2活化的4-异丙基环己烯酮中，而发现未成功添加1,4-具有烯丙基的保护单酚试剂。烯丙基随后通过Pd催化的与烯丙基硼酸酯的偶合而连接至p-，p′-二碘代-双酚环。上述碘化物使用新的方法，用于合成邻的脱碘-选择性ø - ，p -diiodophenols。
• On the Absolute Configuration of Penlanfuran and Related Sesquiterpenoids of the SpongeDysidea fragilis from the North-Brittany Sea
  作者：Ines Mancini、Graziano Guella、Marino Cavazza、Francesco Pietra

  DOI：10.1002/hlca.19900730314

  日期：1990.5.2

  except 11 (+)-2, are of good yield. On the basis of previous chemical transformations, this also establishes the (4R)-configuration for penlanfuran ((−)-1) and other sesquiterpenoids of the sponge Dysidea fragilis from the North-Brittany sea. Non viable routes to (±)-noroxoperlanfuran ((±)-2) are also discussed.

  在Me 3 SiCl存在下，在THF中向溴化（+）-（4 s）-cryptone（（+）- 6）中的1,4-溴化乙烯基溴化镁/ CuBr-SMe 2生成甲硅烷基酚醚7，该甲硅烷基醚7会部分水解在含水后处理中酮8 ; 将残余的7用对甲苯磺酸吡啶鎓（PyT s OH）水解，得到8，将其用乙二醇原位保护，然后进行臭氧处理，得到醛（）-10 。后者在加入3-lithiofuran之后脱水和脱保护。与Py T s OH结合，得到不自然的（4 S）-对映戊烷呋喃的对映体（+）- 2。除了11（+）- 2以外，所有过程的收率都很高。在以前的化学转化的基础上，这也为北布列塔尼海的脆弱海绵状Dydyda的戊兰呋喃（（-）- 1）和其他倍半萜类化合物建立了（4 R）-构型。还讨论了到（±）-诺哌喃呋喃（（±）-2）的不可行路线。
• Total syntheses of (+)-adunctins C and D: assignment of their absolute configurations
  作者：Jian Xiao、Jun Zhao、Ya-Wen Wang、Gan Luo、Yu Peng

  DOI：10.1039/d1ob02055b

  日期：——

  The first total synthesis of (+)-adunctin C (ent-1) and (+)-adunctin D (2), two monoterpene-substitued dihydrochalcones isolated from Piper aduncum (Piperaceae), was achieved. A regioselective oxidative [3 + 2] cycloaddition of acylphloroglucinol with (−)-β-phellandrene was developed to construct their unique spirobenzofuran skeleton. The absolute configurations of natural adunctins 1 and 2 were thus

  (+)-adunctin C ( ent - 1 ) 和 (+)-adunctin D ( 2 ) 是从Piper aduncum (Piperaceae) 中分离出来的两种单萜取代的二氢查尔酮，首次实现了全合成。开发了酰基间苯三酚与 (-)-β-水芹烯的区域选择性氧化 [3 + 2] 环加成，以构建其独特的螺苯并呋喃骨架。因此，通过这些努力分配了天然 adunctins 1和2的绝对构型。
• Trimethylchlorosilane induced ring opening of 2-alkyloxazolidines to enamine derivatives
  作者：Yoshihiko Ito、Masaya Sawamura、Kazuhiko Kominami、Takeo Saegusa

  DOI：10.1016/s0040-4039(00)95022-6

  日期：1985.1

  2-Alkyloxazolidines (5) were ring-opened by trimethylchlorosilane with N,N-diisopropylamine to give N-[2-(trimethylsilyloxy)alkyll-enamines (6). A MgCl2 promoted Michael reaction of chiral enamines thus prepared was achieved with asymmetric induction.

  通过三甲基氯硅烷与N，N-二异丙基胺使2-烷基恶唑烷（5）开环，得到N- [2-（三甲基甲硅烷氧基）烷基-烯胺（6）。由此制备的MgCl 2促进的手性烯胺的迈克尔反应是不对称诱导的。
• Total synthesis of eudesmane terpenes: cyclase phase
  作者：Ke Chen、Yoshihiro Ishihara、María Morón Galán、Phil S. Baran

  DOI：10.1016/j.tet.2010.02.088

  日期：2010.6

  of the lowest oxidized members of the eudesmane family of natural products, is presented. The final synthetic sequence illustrates a nine-step, gram-scale, enantioselective route to this bicyclic terpene with excellent stereocontrol and in 21% overall yield.

  介绍了对二氢junenol的合成努力的全过程，dihydrojunenol是自然产物的eudesmane系列中氧化程度最低的成员之一。最终的合成序列说明了这种双环萜烯的九步克级对映选择性路线，具有出色的立体控制效果，总收率为21％。