(4S,5S)-1-Acetoxy-4-isopropyl-5-methyl-5-vinyl-1-cyclohexene | 128261-61-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (4S,5S)-1-Acetoxy-4-isopropyl-5-methyl-5-vinyl-1-cyclohexene
• 英文别名: (4S,5S)-1-acetoxy-4-isopropenyl-5-methyl-5-vinyl-1-cyclohexene；[(4S,5S)-5-ethenyl-5-methyl-4-prop-1-en-2-ylcyclohexen-1-yl] acetate
• CAS: 128261-61-0
• 化学式: C₁₄H₂₀O₂
• 分子量: 220.312
• InChiKey: VNDYEQFVPWLSFU-UONOGXRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S,5S)-1-Acetoxy-4-isopropyl-5-methyl-5-vinyl-1-cyclohexene 在 aluminum oxide 、 氯化亚砜 作用下， 反应 8.0h， 生成 β-elemenone
  参考文献：
  名称：

  The use of 4,4-disubstituted nopinones for natural-product synthesis. Synthesis of elemanoid sesquiterpenes

  摘要：

  A general and convenient synthetic route to 4,4-disubstituted nopinones 14 from (+)-nopinone (1) is developed and applied to the asymmetric synthesis of some representative elemanoid sesquiterpenes. Phenylsulfenylation of 1 provided sulfide 6 in high yield. A convenient transformation of 6 to 3-(phenylsulfonyl)-4,4-disubstituted-nopinones 13 was accomplished by (i) m-CPBA oxidation of a sulfide compound followed by the Pummerer rearrangement and (ii) the conjugate addition of carbon nucleophiles to the resulting enones, 6 --> 8 --> 9 and 9 --> 10,11 --> 13. Subsequent reductive desulfurization of the adducts 13 provided 14 in good overall yield from 1. Bicyclic ketones 14 are envisioned as promising intermediates for natural product synthesis. As examples, syntheses of two elemanoid sesquiterpenes, beta-elemenone (16) and eleman-8-beta,12-olide (17) in optically active form from (1R,4S,5S)-4,6,6-trimethyl-4-vinylbicyclo[3.1.1]heptan-2-one (14a) were carried out.

  DOI：

  10.1021/jo00025a023
• 作为产物：
  描述：

  (1R,3RS,4S,5R)-4,6,6-Trimethyl-3-(phenylsulfonyl)-4-vinylbicyclo<3.1.1>heptan-2-one 在 三氟化硼乙醚 、 zinc diacetate 、 氨 、 lithium 作用下， 以 乙酸酐 为溶剂， 反应 20.0h， 生成 (4S,5S)-1-Acetoxy-4-isopropyl-5-methyl-5-vinyl-1-cyclohexene
  参考文献：
  名称：

  Kato, Michiharu; Vogler, Bernhard; Tooyama, Youichi, Chemistry Letters, 1990, p. 151 - 154

  摘要：

  DOI：

文献信息

• Practical acetalization and transacetalization of carbonyl compounds catalyzed by recyclable PVP-I
  作者：Di Wang、Fu-Rong Cao、Guangying Lu、Jiangmeng Ren、Bu-Bing Zeng

  DOI：10.1016/j.tet.2021.132250

  日期：2021.7

  A novel PVP-I catalyzed acetalizations/transacetalizations of carbonyl compounds has been developed processing with a mild and easy handling fashion. Different types of Acyclic and cyclic acetals were prepared from carbonyl compounds or their acetals successfully. Further applications of newly developed catalytic combination were testified. This protocol featured with simplicity of operation, mild

  已开发出一种新型 PVP-I 催化羰基化合物的缩醛化/转缩醛化，其处理方式温和且易于处理。以羰基化合物或其缩醛为原料成功制备了不同类型的无环和环状缩醛。证明了新开发的催化组合的进一步应用。该方案具有操作简单、反应条件温和、反应时间短、催化剂可回收利用、底物范围广、收率高等特点。
• Asymmetric Total Synthesis of Onoseriolide, Bolivianine, and Isobolivianine
  作者：Biao Du、Changchun Yuan、Tianzi Yu、Li Yang、Yang Yang、Bo Liu、Song Qin

  DOI：10.1002/chem.201304378

  日期：2014.2.24

  efforts on the total synthesis of bolivianine (1) and isobolivianine (2), involving the synthesis of onoseriolide (3). The first generation synthesis of bolivianine was completed in 21 steps by following a chiral resolution strategy. Based on the potential biogenetic relationship between bolivianine (1), onoseriolide (3), and β‐(E)‐ocimene (8), the second generation synthesis of bolivianine was biomimetically

  在本文中，我们描述了我们在玻利维亚宁（1）和异obolivianine（2）的全合成方面所付出的努力，其中包括onoseriolide（3）的合成。遵循手性拆分策略，分21步完成了第一代玻利维亚宁的合成。基于玻利维亚宁（1），鬼臼内酯（3）和β-（E）-奥美精（8）之间的潜在生物遗传关系），通过14个步骤从市售（+）-马鞭酮仿生实现了玻利维亚宁的第二代合成。改进的总合成功能包括通过烯丙基金属碳烯进行钯催化的前所未有的钯催化的分子内环丙烷化，用于构建ABC三环系统，以及用于安装EFG的Diels–Alder /分子间杂Diels–Alder（DA / IMHDA）级联反应具有正确立体化学的三环骨架。在酸的存在下促进了从玻利维亚宁向异obolivianine的转化。生物合成机制和优秀的区域选择性和内选择性级联由理论化学基础上的理论计算很好的支持。
• Total Syntheses of Sarcandrolide J and Shizukaol D: Lindenane Sesquiterpenoid [4+2] Dimers
  作者：Changchun Yuan、Biao Du、Heping Deng、Yi Man、Bo Liu

  DOI：10.1002/anie.201610484

  日期：2017.1.9

  The syntheses of members of a family of lindenane sesquiterpenoid [4+2] dimers led to the total syntheses of sarcandrolide J and shizukaol D. Inspired by a modified biosynthetic pathway, a cascade featuring furan formation/alkene isomerization/Diels–Alder cycloaddition was devised to construct the congested polycyclic architecture of the target molecules with the correct stereochemistry. This study

  茚满倍半萜类 [4+2] 二聚体家族成员的合成导致了 sarcandrolide J 和 Shizukaol D 的全合成。 受改良的生物合成途径的启发，设计了以呋喃形成/烯烃异构化/Diels-Alder 环加成为特征的级联反应以正确的立体化学构建目标分子的拥塞多环结构。这项研究为这一天然产物家族开辟了开创性的合成入口，并为充分探索其生物学功能铺平了道路。
• Total synthesis, structural revision and biological evaluation of γ-elemene-type sesquiterpenes
  作者：Changchun Yuan、Shangyong Zhong、Xingyi Li、Yanhong Wang、Miao-Miao Xun、Yunli Bai、Kongkai Zhu

  DOI：10.1039/c8ob02005a

  日期：——

  Total synthesis and absolute configuration confirmation of γ-elemene-type sesquiterpenes, which possess vast potential for biological activities, was investigated based on a convergent synthetic strategy. A key intermediate with all functional groups of this family of natural products was accessed by an intermolecular aldol reaction and then an acetylation of a known ketone (12) derived from commercially

  基于聚合合成策略，研究了具有巨大生物活性潜力的γ-榄香烯型倍半萜的全合成和绝对构象确证。通过分子间的醇醛缩合反应，然后对衍生自市售马鞭草酮的已知酮（12）进行乙酰化，可以得到具有该天然产物家族的所有官能团的关键中间体。通过在不同溶剂中控制碱促进的环化操作，可以轻松地将通用中间体转变为结构上不同的γ-榄香烯型倍半萜。ElEMa-1,3,7（11），8-tetraen-8,12-lactam（4'）和8β-甲氧基-isogermafurenolide（6a）的首次合成说明了这种鲁棒方法的实用性），以及仅6或7个步骤即可合成elEM-1,3,7,8-四烯-8,12-内酰胺（3）和羟基异二十二烯呋喃内酯（5）。此外，的结构报道5β ħ -elEM-1,3,7,8四烯-8,12-内酯（1）中的溶液修改为ELEM-1,3,7,8四烯8,12-通过比较其确定的基准，发现olide（3），并且elEMa-1
• Bioinspired Total Synthesis of Bolivianine: A Diels– Alder/Intramolecular Hetero-Diels–Alder Cascade Approach
  作者：Changchun Yuan、Biao Du、Li Yang、Bo Liu

  DOI：10.1021/ja4040335

  日期：2013.6.26

  We report the first total synthesis of bolivanine in a 14 step pathway involving the synthesis of onoseriolide. Our synthesis features a palladium-catalyzed intramolecular cyclopropanation involving an allylic metal carbene and a Diels-Alder/intramolecular hetero-Diels-Alder cascade, allowing the single-step assembly of a tricyclic system with proper configuration. The synthetic efforts validate our modified biogenetic hypothesis and allow us to confirm the absolute configuration of bolivianine.