(S,E)-2,2-dimethyl-4-styryl-1,3-dioxolane | 147976-19-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S,E)-2,2-dimethyl-4-styryl-1,3-dioxolane
• 英文别名: (4S)-2,2-dimethyl-4-[(E)-2-phenylethenyl]-1,3-dioxolane
• CAS: 147976-19-0
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: CHIBTVUJLKHUMW-BCPZQOPPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  (S,E)-2,2-dimethyl-4-styryl-1,3-dioxolane 在 palladium on activated charcoal 吡啶 、 咪唑 、 dirhodium tetraacetate 、 甲酸 、 氯磺酰异氰酸酯 、 碘苯二乙酸 、 氢气 、 magnesium oxide 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 tert-butyl-[[(4R,6S)-2,2-dioxo-4-phenyloxathiazinan-6-yl]methoxy]-diphenylsilane
  参考文献：
  名称：

  Stereoselective synthesis of the 1,N2-deoxyguanosine adducts of cinnamaldehyde. A stereocontrolled route to deoxyguanosine adducts of α,β-unsaturated aldehydes

  摘要：

  alpha,beta-Unsaturated aldehydes (enals) react with deoxyguanosine and have mutagenic potential. For higher enals, the reaction of deoxyguanosine gives diastereomeric 6-substituted 8-hydroxypyrimidopurinone products. These stereoisomers may have different local conformations in DNA, which may have biological consequences. We have developed a stereospecific synthesis of 1, N-2-deoxyguanosine adducts of cinnamaldehyde. The key step is the synthesis is a metal-promoted intramolecular C-H insertion reaction of nitrogen of an enantiomerically pure sulfamate ester. The approach may be general for the stereocontrolled synthesis of this class of DNA adducts and can be applied to the preparation of site-specifically adducted oligonucleotides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.006
• 作为产物：
  描述：

  苄基三苯基氯化膦 、 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 正丁基锂 作用下， 以80%的产率得到(S,E)-2,2-dimethyl-4-styryl-1,3-dioxolane
  参考文献：
  名称：

  Stereoselective synthesis of the 1,N2-deoxyguanosine adducts of cinnamaldehyde. A stereocontrolled route to deoxyguanosine adducts of α,β-unsaturated aldehydes

  摘要：

  alpha,beta-Unsaturated aldehydes (enals) react with deoxyguanosine and have mutagenic potential. For higher enals, the reaction of deoxyguanosine gives diastereomeric 6-substituted 8-hydroxypyrimidopurinone products. These stereoisomers may have different local conformations in DNA, which may have biological consequences. We have developed a stereospecific synthesis of 1, N-2-deoxyguanosine adducts of cinnamaldehyde. The key step is the synthesis is a metal-promoted intramolecular C-H insertion reaction of nitrogen of an enantiomerically pure sulfamate ester. The approach may be general for the stereocontrolled synthesis of this class of DNA adducts and can be applied to the preparation of site-specifically adducted oligonucleotides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.08.006

文献信息

• Diastereoselective Fluorocyclopropanation of Chiral Allylic Alcohols Using an α-Fluoroiodomethylzinc Carbenoid
  作者：Chandrasekhar Navuluri、André B. Charette

  DOI：10.1021/acs.orglett.5b02097

  日期：2015.9.4

  Chiral fluorocyclopropyl carbinols were synthesized in high diastereoselectivities via a zinc mediated cyclopropanation reaction, using sec-allylic alcohols as simple building blocks. An enantioselective version of this transformation was achieved through in situ formation of chiral allylic zinc sec-alkoxides from the requisite aldehydes using Walsh’s protocol.

  使用仲烯丙基醇作为简单的结构单元，通过锌介导的环丙烷化反应，以高非对映选择性合成了手性氟代环丙基甲醇。该转化的对映选择性形式是通过使用沃尔什（Walsh）方案从所需醛中原位形成手性烯丙基仲仲醇盐来实现的。
• The influence of α-coordinating groups of aldehydes on <i>E</i>/<i>Z</i>-selectivity and the use of quaternary ammonium counter ions for enhanced <i>E</i>-selectivity in the Julia–Kocienski reaction
  作者：Mintu Rehman、Sravya Surendran、Nagendra Siddavatam、Goreti Rajendar

  DOI：10.1039/d1ob02126e

  日期：——

  Modified reaction conditions for improved E-selectivity of olefins in the Julia–Kocienski reaction of aldehydes having α-coordinating substituents are demonstrated. The chelating groups in aldehydes are expected to stabilize the syn-transition state with metal ions, whereas the weakly coordinating quaternary ammonium ions are devoid of all possible chelating interactions to enhance E-selectivity. A

  证明了在具有 α- 配位取代基的醛的 Julia-Kocienski 反应中改进的烯烃E选择性的改进反应条件。醛中的螯合基团有望稳定与金属离子的顺过渡态，而弱配位的季铵离子没有所有可能的螯合相互作用以增强E选择性。提出了一项系统研究，以研究醛的相邻保护基团的大小及其对 Julia-Kocienski 反应中E / Z选择性的螯合效应。
• Two simple and alternative approaches for the synthesis of anticancer active goniothalamin
  作者：Manchala Narasimhulu、S. Siva Prasad、Rama Moorthy Appa、Jangam Lakshmidevi、Katta Venkateswarlu

  DOI：10.24820/ark.5550190.p010.461

  日期：——

  Two alternative and straightforward routes were developed for the construction of (R)-goniothalamin, a natural anticancer agent. The first method starts with (R)-glycidol involving stereoselective (partial) reduction of alkyne and sulfoxide Julia-Lythgoe olefination as key steps. Second method deals with the synthesis of (R)goniothalamin from 2,3-O-isopropylidene-D-glyceraldehyde with partial reduction

  为构建 (R)-goniothalamin（一种天然抗癌剂）开发了两种替代且直接的途径。第一种方法从 (R)-缩水甘油开始，包括炔烃和亚砜 Julia-Lythgoe 烯化的立体选择性（部分）还原作为关键步骤。第二种方法涉及从 2,3-O-异亚丙基-D-甘油醛合成 (R)goniothalamin，其中部分还原腈和 Still-Gennari 立体选择性烯化作为关键步骤。这两种标准有机反应顺序简单的方法可用于有机化学二、三年级课程。
• Total Synthesis of a Mevinic Acid Analog
  作者：Thummalapally Srikanth Reddy、Dorigondla Kumar Reddy、Manchala Narasimhulu、Dasari Ramesh、Yenamandra Venkateswarlu

  DOI：10.1002/hlca.201000062

  日期：2010.11

  Total synthesis of mevinic acid analog 1 has been achieved efficiently starting from chiral 2,3‐O‐isopropylidene‐D‐glyceraldehyde (2). The synthesis involves Mitsunobu reaction and Evans' intramolecular oxa‐Michael syn‐addition reactions as key steps.

  从手性2,3- O-异亚丙基-D-甘油醛（2）开始已成功实现了全酸类似物1的全合成。合成涉及Mitsunobu反应和Evans的分子内oxa- Michael合成加成反应作为关键步骤。
• PROCESS FOR PREPARATION OF 13,14-DIHYDRO-PGF2 ALPHA DERIVATIVES
  申请人：MARTYNOW Jacek

  公开号：US20080207926A1

  公开（公告）日：2008-08-28

  The invention relates to a process for the preparation of 13,14-dihydro-PGF 2α derivatives of R or S configuration at carbon 15, represented by the general formula (I), wherein the identity of the substituents is defined in the description. Compounds of the formula (I) are valuable biologically-active substances or intermediates in the preparation thereof. The invention especially relates to the process for preparation of 13,14-dihydro-15(R)-17-substituted-18,19,20-trinor-PGF 2α , i.e., latanoprost.

  本发明涉及一种制备在碳15处具有R或S构型的13,14-二氢-PGF2α衍生物的方法，该衍生物由通式（I）表示，其中置换基的身份在说明中定义。式（I）化合物是有价值的生物活性物质或制备中间体。本发明特别涉及制备13,14-二氢-15（R）-17-取代-18,19,20-三去甲-PGF2α，即拉坦前列素的方法。