(2E,6E)-octa-2,6-diendioic acid di-tert-butyl diester | 679436-07-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2E,6E)-octa-2,6-diendioic acid di-tert-butyl diester
• 英文别名: (2E,6E)-octa-2,6-dienedioic acid di-tert-butyl ester；di-tert-butyl (E,E)-octa-2,6-diendioate；ditert-butyl (2E,6E)-octa-2,6-dienedioate
• CAS: 679436-07-8
• 化学式: C₁₆H₂₆O₄
• 分子量: 282.38
• InChiKey: MWKZATUIDCSXCP-WGDLNXRISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  (2E,6E)-octa-2,6-diendioic acid di-tert-butyl diester 在 palladium on activated charcoal 正丁基锂 、 氢气 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 溶剂黄146 为溶剂， -78.0~20.0 ℃ 、506.66 kPa 条件下， 反应 29.0h， 生成 di-tert-butyl (1S,2R,5S)-2-amino-5-carboxymethyl-cyclopentane-1-carboxylate
  参考文献：
  名称：

  Asymmetric synthesis of the stereoisomers of 2-amino-5-carboxymethyl-cyclopentane-1-carboxylate

  摘要：

  2-氨基-5-羧甲基环戊烷-1-羧酸酯的立体异构体可以通过对(E,E)-辛烯-2,6-二羧酸的二酯衍生物进行立体选择性合成，关键步骤是利用手性锂N-苄基-N-α-甲基苄胺的共轭加成。trans-C(1)–C(2)-立体异构体通过与锂(R)-N-苄基-N-α-甲基苄胺的非对映选择性串联共轭加成环化反应容易制备，随后进行氢解和酯水解，从而良好收率地得到(1R,2R,5R)-和(1R,2R,5S)-β-氨基二酸。cis-C(1)–C(2)-立体异构体的制备涉及N-氧化和主要的由共轭加成和环化反应生成的非对映异构体的科普消除反应，得到手性(R)-5-羧甲基环戊烯-1-羧酸酯。无论是锂(R)-还是(S)-N-苄基-N-α-甲基苄胺与(R)-5-羧甲基环戊烯-1-羧酸酯进行的共轭加成，经过2,6-二-tert-丁基苯酚的非对映选择性质子化后，经过氢解和酯水解，能够以良好收率得到(1S,2R,5R)-和(1R,2S,5R)-β-氨基二酸。在初始的共轭加成和环化反应中使用(S)-N-苄基-N-α-甲基苄胺，并随后重复消除和共轭加成策略，可以立体选择性地获得所有2-氨基-5-羧甲基环戊烷-1-羧酸酯的立体异构体。

  DOI：

  10.1039/b313386a
• 作为产物：
  描述：

  1,5-已二烯 、 丙烯酸叔丁酯 在 M₇₃SIPr 作用下， 以 氯仿 为溶剂， 100.0 ℃ 、200.0 kPa 条件下， 反应 1.0h， 以88%的产率得到(2E,6E)-octa-2,6-diendioic acid di-tert-butyl diester
  参考文献：
  名称：

  Step-Economical Access to Valuable Weinreb Amide 2,5-Disubstituted Pyrrolidines by a Sequential One-Pot Two-Directional Cross-Metathesis/Cyclizing Aza-Michael Process

  摘要：

  Double cross-metathesis of 1,5-hexadiene with a variety of electron-deficient alkenes including the reluctant Weinreb acrylamide has been successfully accomplished. It was found that the process is quite general, and microwave irradiation effectively accelerates cross-coupling metathesis. This promotes a very versatile and high yielding methodology for the synthesis of symmetric Michael acceptors, which can be transformed into 2,5-disubstituted pyrrolidines through a sequential one-pot two-directional cross-metathesis/ring-closing double aza-Michael process.

  DOI：

  10.1021/jo302435a

文献信息

• A Novel Strategy Towards the Asymmetric Synthesis of Orthogonally Funtionalised 2-N-Benzyl-N-α-methylbenzylamino- 5-carboxymethyl-cyclopentane-1-carboxylic acid.
  作者：Narciso Garrido、Mohamed El Hammoumi、David Díez、Mercedes García、Julio Urones

  DOI：10.3390/90500373

  日期：——

  The asymmetric synthesis of the orthogonally funtionalised compounds tert-butyl 2-N-benzyl-N-α-methylbenzylamino-5-methoxycarbonylmethylcyclopentane- 1-carboxylate and methyl 2-N-benzyl-N-α-methylbenzylamino-5–carboxymethylcyclo- pentane-1-carboxylate by a domino reaction of tert-butyl methyl (E,E)-octa-2,6- diendioate with lithium N-α-methylbenzyl-N-benzylamide initiated by a Michael addition, subsequent 5-exo-trig intramolecular cyclisation and posterior selective hydrolysis with trifluoroacetic acid is reported.

  正交官能化化合物叔丁基2-N-苯甲基-N-α-甲基苯甲基氨基-5-甲氧基羰基甲基环戊烷-1-羧酸酯和甲基2-N-苯甲基-N-α-甲基苯甲基氨基-5-羧甲基环戊烷-的不对称合成通过叔丁基甲基 (E,E)-八-2,6-二烯二酸酯与 N-α-甲基苄基-N-苄基酰胺锂的多米诺反应生成 1-羧酸酯，该反应由 Michael 加成引发，随后进行 5-exo-trig 分子内环化并报道了用三氟乙酸进行后选择性水解。
• Rapid and Efficient Access to Meso-2,5-cis-disubstituted Pyrrolidines by Double Aza-Michael Reactions of Chiral Primary Amines
  作者：Delphine Joseph、Leila Cabral dos Santos、Zineb Bahlaouan、Khadija El Kassimi、Claire Troufflard、Sandrine Delarue-Cochin、Mohamed Zahouily

  DOI：10.3987/com-07-s(u)56

  日期：——
• Asymmetric synthesis of the stereoisomers of 2-amino-5-carboxymethyl-cyclopentane-1-carboxylate
  作者：Julio G. Urones、Narciso M. Garrido、David Díez、Mohamed M. El Hammoumi、Sara H. Dominguez、J. Antonio Casaseca、Stephen G. Davies、Andrew D. Smith

  DOI：10.1039/b313386a

  日期：——

  The stereoisomers of 2-amino-5-carboxymethyl-cyclopentane-1-carboxylate may be prepared stereoselectively from diester derivatives of (E,E)-octa-2,6-diendioc acid, with the key step utilising the conjugate addition of homochiral lithium N-benzyl-N-α-methylbenzylamide. The trans-C(1)–C(2)-stereoisomers are readily prepared via a diastereoselective tandem conjugate addition cyclisation protocol with lithium (R)-N-benzyl-N-α-methylbenzylamide, with subsequent hydrogenolysis and ester hydrolysis giving the (1R,2R,5R)- and (1R,2R,5S)-β-amino diacids in good yields. The preparation of the cis-C(1)–C(2)-stereoisomers utilises a protocol involving N-oxidation and Cope elimination of the major diastereoisomeric product arising from conjugate addition and cyclisation, giving homochiral (R)-5-carboxymethyl-cyclopentene-1-carboxylate. Conjugate addition of either lithium (R)- or (S)-N-benzyl-N-α-methylbenzylamide to (R)-5-carboxymethyl-cyclopentene-1-carboxylate, and diastereoselective protonation with 2,6-di-tert-butyl phenol gives, after hydrogenolysis and ester hydrolysis, the (1S,2R,5R)- and (1R,2S,5R)-β-amino diacids in good yield. The use of (S)-N-benzyl-N-α-methylbenzylamide in the initial conjugate addition and cyclisation reaction, and subsequent repetition of the elimination and conjugate addition strategy allows stereoselective access to all stereoisomers of 2-amino-5-carboxymethyl-cyclopentane-1-carboxylate.

  2-氨基-5-羧甲基环戊烷-1-羧酸酯的立体异构体可以通过对(E,E)-辛烯-2,6-二羧酸的二酯衍生物进行立体选择性合成，关键步骤是利用手性锂N-苄基-N-α-甲基苄胺的共轭加成。trans-C(1)–C(2)-立体异构体通过与锂(R)-N-苄基-N-α-甲基苄胺的非对映选择性串联共轭加成环化反应容易制备，随后进行氢解和酯水解，从而良好收率地得到(1R,2R,5R)-和(1R,2R,5S)-β-氨基二酸。cis-C(1)–C(2)-立体异构体的制备涉及N-氧化和主要的由共轭加成和环化反应生成的非对映异构体的科普消除反应，得到手性(R)-5-羧甲基环戊烯-1-羧酸酯。无论是锂(R)-还是(S)-N-苄基-N-α-甲基苄胺与(R)-5-羧甲基环戊烯-1-羧酸酯进行的共轭加成，经过2,6-二-tert-丁基苯酚的非对映选择性质子化后，经过氢解和酯水解，能够以良好收率得到(1S,2R,5R)-和(1R,2S,5R)-β-氨基二酸。在初始的共轭加成和环化反应中使用(S)-N-苄基-N-α-甲基苄胺，并随后重复消除和共轭加成策略，可以立体选择性地获得所有2-氨基-5-羧甲基环戊烷-1-羧酸酯的立体异构体。
• Step-Economical Access to Valuable Weinreb Amide 2,5-Disubstituted Pyrrolidines by a Sequential One-Pot Two-Directional Cross-Metathesis/Cyclizing Aza-Michael Process
  作者：Hamza Boufroura、Marc Mauduit、Emmanuelle Drège、Delphine Joseph

  DOI：10.1021/jo302435a

  日期：2013.3.15

  Double cross-metathesis of 1,5-hexadiene with a variety of electron-deficient alkenes including the reluctant Weinreb acrylamide has been successfully accomplished. It was found that the process is quite general, and microwave irradiation effectively accelerates cross-coupling metathesis. This promotes a very versatile and high yielding methodology for the synthesis of symmetric Michael acceptors, which can be transformed into 2,5-disubstituted pyrrolidines through a sequential one-pot two-directional cross-metathesis/ring-closing double aza-Michael process.