acrolein gem-dibenzoate | 1208092-25-4

• 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: acrolein gem-dibenzoate
• 英文别名: prop-2-ene-1,1-diyl dibenzoate；1-Benzoyloxyprop-2-enyl benzoate
• CAS: 1208092-25-4
• 化学式: C₁₇H₁₄O₄
• 分子量: 282.296
• InChiKey: RZVGMJCLOAOYEG-UHFFFAOYSA-N

物化性质

• 沸点：
  428.4±33.0 °C(Predicted)
• 密度：
  1.185±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  acrolein gem-dibenzoate 、 正己醛 在 potassium phosphate 、 [(R)-(+)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole][4-cyano-3-nitrobenzenecarboxylato] [1,2,3-eta-2-propenyl Ir(III)] 作用下， 以 四氢呋喃 、 异丙醇 为溶剂， 反应 52.0h， 以47%的产率得到(3R,4S)-3-benzoyloxynon-1-en-4-ol
  参考文献：
  名称：

  Enantioselective synthesis of (+)-aspercyclide A

  摘要：

  An efficient synthesis of the natural IgE-Fc epsilon RI PPI inhibitor (+)-aspercyclide A (1) was achieved through the use of a Krische iridium-catalyzed diastereo- and enantioselective alkoxyallylation to form the key mono-protected anti-diol intermediate 4, in high optical purity. A derivative of the natural product (15), containing an oxathiazine dioxide ring in place of the ring-A hydroxyaldehyde unit has also been prepared and found to display comparable ELISA activity to the parent compound, indicating that the aldehyde group is not the key determinant of activity. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.07.038
• 作为产物：
  描述：

  苯甲酸酐 、 丙烯醛 在 硫酸 作用下， 以 二氯甲烷 为溶剂， 以50%的产率得到acrolein gem-dibenzoate
  参考文献：
  名称：

  Diastereo- and Enantioselective anti-Alkoxyallylation Employing Allylic gem-Dicarboxylates as Allyl Donors via Iridium-Catalyzed Transfer Hydrogenation

  摘要：

  Enantioselective transfer hydrogenation of gem-dibenzoate le in the presence of aromatic. alpha,beta-unsaturated, or aliphatic aldehydes 2a-i mediated by isopropyl alcohol and employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, 4-cyano-3-nitrobenzoic acid, and (R)-SEGPHOS delivers products Of alkoxyallylation 3a-i, 4a, 4e, 4f, and 4i in good isolated yields (62-82%) with good to excellent diastereoselectivities (7:1 to 18:1 dr) and exceptional enantioselectivities (90-99% ee). This protocol provides an alternative to the Use of premetalated nucleophiles in carbonyl alkoxyallylation.

  DOI：

  10.1021/ja9097675

文献信息

• [EN] PROCESS FOR THE PREPARATION OF BETA-SANTALOL<br/>[FR] PROCÉDÉ DE PRÉPARATION DU BÊTA-SANTALOL
  申请人：FIRMENICH & CIE

  公开号：WO2013001026A1

  公开（公告）日：2013-01-03

  The present invention concerns a process for the preparation of a compound of formula (I) in the form of any one of its stereoisomers or mixtures thereof, and wherein R represents a C2-C10 group of formula CORa wherein Ra is an alkyl or alkenyl group optionally comprising one or two ether functional groups or is a phenyl or benzyl group optionally substituted by one to three alkyl, alkoxyl, carboxyl, acyl, amino or nitro groups or halogen atoms. The invention concerns also the use of compound (I) for the synthesis of β-santalol or of derivatives thereof.

  本发明涉及一种制备式(I)化合物的过程，其形式为其立体异构体之一或其混合物，其中R代表具有CORa式的C2-C10基团，其中Ra是一种烷基或烯基基团，可选地包括一个或两个醚功能基团，或者是一种苯基或苄基基团，可选地被一个到三个烷基、烷氧基、羧基、酰基、氨基或硝基基团或卤原子取代。该发明还涉及化合物(I)用于合成β-香檀醇或其衍生物的用途。
• Enantioselective Synthesis of <i>des</i>-Epoxy-Amphidinolide N
  作者：Barry M. Trost、Wen-Ju Bai、Craig E. Stivala、Christoph Hohn、Caroline Poock、Marc Heinrich、Shiyan Xu、Jullien Rey

  DOI：10.1021/jacs.8b11827

  日期：2018.12.12

  efforts addressed the scalability problem of the southern fragment synthesis and significantly improved the efficiency of the atom-economical Ru AA coupling, but suffered from several protecting group-based issues that proved insurmountable. Finally, relying on a judicious protecting group strategy together with concise fragment preparation, des-epoxy-amphidinolide N was achieved in a convergent fashion

  des-epoxy-amphidinolide N 的合成在 22 个最长的线性步骤和 33 个总步骤中实现。本文报道了三代合成努力。在第一代中，我们的关键拼接策略突出了分子内 Ru 催化的烯烃 - 炔 (Ru AA) 偶联和后期环氧化，证明是成功的，但使用二羟基化方法安装 α,α'-二羟基酮基序有问题。我们的第二代合成工作解决了南片段合成的可扩展性问题，并显着提高了原子经济 Ru AA 偶联的效率，但遇到了几个基于保护基的问题，这些问题被证明是无法克服的。最后，依靠明智的保护组策略以及简洁的片段准备，des-epoxy-amphidinolide N 以收敛的方式实现。计算揭示了amphidinolide N 内的氢键桥。使用我们合成的脱环氧-amphidinolide N 比较13C NMR 化学位移差异表明amphidinolide N 和carbenolide I 可能相同。
• PROCESS FOR THE PREPARATION OF BETA-SANTALOL
  申请人：Firmenich SA

  公开号：EP2726447A1

  公开（公告）日：2014-05-07
• US9056826B2
  申请人：——

  公开号：US9056826B2

  公开（公告）日：2015-06-16
• Diastereo- and Enantioselective <i>anti</i>-Alkoxyallylation Employing Allylic <i>gem</i>-Dicarboxylates as Allyl Donors via Iridium-Catalyzed Transfer Hydrogenation
  作者：Soo Bong Han、Hoon Han、Michael J. Krische

  DOI：10.1021/ja9097675

  日期：2010.2.17

  Enantioselective transfer hydrogenation of gem-dibenzoate le in the presence of aromatic. alpha,beta-unsaturated, or aliphatic aldehydes 2a-i mediated by isopropyl alcohol and employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, 4-cyano-3-nitrobenzoic acid, and (R)-SEGPHOS delivers products Of alkoxyallylation 3a-i, 4a, 4e, 4f, and 4i in good isolated yields (62-82%) with good to excellent diastereoselectivities (7:1 to 18:1 dr) and exceptional enantioselectivities (90-99% ee). This protocol provides an alternative to the Use of premetalated nucleophiles in carbonyl alkoxyallylation.