ethyl 1,4-pentadien-3-yl carbonate | 116997-87-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: ethyl 1,4-pentadien-3-yl carbonate
• 英文别名: ethyl-1,4-pentadien-3-yl carbonate；Ethyl penta-1,4-dien-3-yl carbonate
• CAS: 116997-87-6
• 化学式: C₈H₁₂O₃
• 分子量: 156.181
• InChiKey: PPBNDJRVAWBHER-UHFFFAOYSA-N

物化性质

• 沸点：
  173.3±29.0 °C(Predicted)
• 密度：
  0.970±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 1,4-pentadien-3-yl carbonate 在 tris-(dibenzylideneacetone)dipalladium(0) 、 1,2-双(二苯基膦)乙烷 作用下， 以 四氢呋喃 为溶剂， 反应 19.0h， 生成
  参考文献：
  名称：

  Ti/Pd-promoted intramolecular Michael-type addition of allylic carboxylates to activated alkenes

  摘要：

  报道了一种有趣的方案，用于合成不同乙烯基取代的碳环和杂环，该方案基于使用烯丙基羧酸酯作为亲核试剂的新分子内迈克尔型反应。催化过程的成功基于后过渡金属（钯）和自由基试剂（钛）之间的良好配合。

  DOI：

  10.1039/c1cc14573h

文献信息

• Chiral 3,6-Dihydro-2H-1,4-oxazin-2-ones as Alanine Equivalents for the Asymmetric Synthesis of α-Methyl α-Amino Acids (AMAAs) under Mild Reaction Conditions
  作者：Rafael Chinchilla、Nuria Galindo、Carmen Nájera

  DOI：10.1055/s-1999-3456

  日期：1999.4

  3,6-Dihydro-2H-1,4-oxazin-2-ones 1 act as very reactive chiral cyclic alanine equivalents and can be diastereoselectively alkylated or allylated using mild reaction conditions: potassium carbonate under phase-transfer catalysis (PTC) conditions when using activated alkyl halides, organic bases such as tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) when using unactivated alkyl halides, and neutral Pd(0)-catalysis when allylic carbonates are used. In most cases, the diastereoselectivity under all these different reaction conditions is excellent although the reactions are always carried out at room temperature. Hydrolysis of the obtained alkylated or allylated oxazinones allows the preparation of enantiomerically enriched (S)-α-methyl α-amino acids (S)-AMAAs. The PTC and organic base methodologies have also been applied to the synthesis of (R)-α-methyl α-amino acids starting from (R)-alanine. When dihalides are used as electrophiles under PTC or BEMP conditions, a spontaneous N-alkylation also takes place giving bicyclic oxazinones, which can be hydrolyzed to enantiomerically pure cyclic (S)-AMAAs.

  3,6-二氢-2H-1,4-噁嗪-2-酮1作为非常活泼的手性环状丙氨酸等价物，可以在温和反应条件下进行立体选择性烷基化或烯丙基化：使用活化烷基卤化物时，在相转移催化（PTC）条件下使用碳酸钾；使用非活化烷基卤化物时，使用如叔丁基亚氨基-2-二乙氨基-1,3-二甲基过氢-1,3,2-二氮磷烷（BEMP）或1,8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）等有机碱；使用烯丙基碳酸盐时，使用中性零价钯催化。在大多数情况下，尽管反应总是在室温下进行，但在所有这些不同反应条件下，立体选择性都非常优异。所得的烷基化或烯丙基化噁嗪酮的水解可以制备具有光学活性的（S）-α-甲基α-氨基酸（S）-AMAA。PTC和有机碱方法也已应用于从（R）-丙氨酸开始合成（R）-α-甲基α-氨基酸。当使用二卤化物作为亲电试剂在PTC或BEMP条件下时，也会自发发生N-烷基化，生成双环噁嗪酮，其可以水解为具有高光学纯度的环状（S）-AMAA。
• A highly efficient and practical preparation of 2,4-pentadienyltitaniums and their γ-selective addition reaction with aldehydes and ketones
  作者：Sentaro Okamoto、Fumie Sato

  DOI：10.1016/s0022-328x(00)00911-6

  日期：2001.4

  were readily prepared from a divalent titanium reagent, Ti(O–i-Pr)4/2i-PrMgCl, and penta-1,4-dien-3-ol or penta-2,4-dien-1-ol derivatives, and the organotitaniums thus prepared reacted with aldehydes and ketones smoothly to afford the corresponding penta-1,4-dien-3-yl carbinols highly predominantly in excellent yield.

  被容易地从二价钛试剂制备的各种戊-2,4- dienyltitanium复合物，包括那些具有一个官能团的，钛（O-我-Pr）4 /2我-PrMgCl，和五-1,4- dien- 3-ol或五-2,4-二烯-1-醇衍生物以及如此制得的有机钛与醛和酮平稳反应，从而以优异的收率非常主要地提供相应的五-1,4-二烯-3-基甲醇。
• Asymmetric Synthesis ofα-Methylα-Amino Acids by Diastereoselective Alkylation of Optically Active 6-Isopropyl-3-methyl-2,3—dihydro-6H-1,4-oxazin-2-ones
  作者：Rafael Chinchilla、Larry R. Falvello、Nuria Galindo、Carmen Nájera

  DOI：10.1002/anie.199709951

  日期：1997.5.16
• N-Boc-α-tosylsarcosine ethyl ester: An α-amido sulfone for the regio- and stereoselective synthesis of protected γ,δ-unsaturated N-methyl-α-amino acids by palladium-catalyzed nucleophilic substitution
  作者：Diego A. Alonso、Ana Costa、Carmen Nájera

  DOI：10.1016/s0040-4039(97)10054-5

  日期：1997.11

  N-Boc-alpha-tosylsarcosine ethyl ester (3) reacts under neutral conditions either with allylic carbonates or with vinyloxirane in the presence of a catalytic amount of Pd(PPh3)(4) and dppe (5 mol%) to give regio- and stereoselectively the corresponding allylated products 5 and 6, respectively. Reductive desulfonylation of these compounds with Mg-MeOH affords the corresponding protected gamma,delta-unsaturated N-methyl-alpha-amino acids 7 and 8. (C) 1997 Elsevier Science Ltd.
• Ti(II)-Mediated Tandem Inter- and Intramolecular Coupling Reaction of Unsaturated Hydrocarbons:  One-Pot Preparation of Cyclopentanes and Cyclohexanes from Readily Available Acyclic Starting Materials
  作者：Sentaro Okamoto、Kandasamy Subburaj、Fumie Sato

  DOI：10.1021/ja0155837

  日期：2001.5.1