dimethyl (E,E)-octa-2,6-diendioate | 26505-44-2

• 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: dimethyl (E,E)-octa-2,6-diendioate
• 英文别名: (2E,6E)-octa-2,6-dienedioic acid dimethyl ester；dimethyl trans,trans-octa-2,6-diene-1,8-dioate；(E,E)-dimethyl 2,6-octadiene-1,8-dioate；E,E-dimethyl octa-2,6-dienedioate；octa-2t,6t-dienedioic acid dimethyl ester；trans,trans-Octa-2,6-dien-1,8-dicarbonsaeuredimethylester；dimethyl (2E,6E)-octa-2,6-dienedioate
• CAS: 26505-44-2
• 化学式: C₁₀H₁₄O₄
• 分子量: 198.219
• InChiKey: AISQNSQBYXPSBT-KQQUZDAGSA-N

物化性质

• 沸点：
  95 °C(Press: 0.15 Torr)
• 密度：
  1.055±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  dimethyl (E,E)-octa-2,6-diendioate 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 trans,trans-2,6-octadiene-1,8-diol
  参考文献：
  名称：

  Conformational effects on the 2,3-sigmatropic shift of sulfur-stabilized ylides and enolates involving bicyclic transition states

  摘要：

  DOI：

  10.1021/jo01332a029
• 作为产物：
  描述：

  2,7-dibromooctanedioic acid dimethyl ester 以 N,N-二甲基甲酰胺 为溶剂， 生成 dimethyl (E,E)-octa-2,6-diendioate
  参考文献：
  名称：

  Solution photochemistry. X. Effects of double-bond geometry and of increasing double-bond separation on the photochemical reactions of acyclic nonconjugated dienes

  摘要：

  DOI：

  10.1021/jo00799a021

文献信息

• Coupling reactions of vinylketene silyl acetals promoted by titanium tetrachloride
  作者：Kenji Hirai、Iwao Ojima

  DOI：10.1016/s0040-4039(00)81527-0

  日期：1983.1

  Homo- and cross-couplings of vinylketene silyl acetals were found to be effectively promoted by titanium tetrachloride to give the corresponding unsaturated diesters in good yields. The reactions between two different ketene silyl acetate afforded the corresponding cross-coupling products in unexpectedly good selectivities.

  发现四氯化钛可有效地促进乙烯酮甲硅烷基乙缩醛的均相和交叉偶联，从而以良好的收率得到相应的不饱和二酯。两种不同的乙烯酮乙酸乙烯酯之间的反应以出乎意料的良好选择性提供了相应的交叉偶联产物。
• X=Y-ZH systems as potential 1,3-dipoles. Part 34. generation of nitrones from oximes. Tandem michael addition-1,3-dipolar cycloaddition reactions. class 2 processes utilising bifunctional michael acceptor-dipolarophile components.
  作者：Ronald Grigg、Michael J. Dorrity、Frances Heaney、John F. Malone、Shuleewan Rajviroongit、Visuvanathar Sridharan、Sivagnanasundram Surendrakumar

  DOI：10.1016/s0040-4020(01)91022-1

  日期：1991.9

  Aldoximes and ketoximes react with a range of bifunctional Michael acceptor-dipolarophile substrates comprising functionalised 1,3-, 1,4- and 1,5-dienes via a tandem process involving an N-alkenyl nitrone intermediate. The 1,3-dienes react regio- and stereo-specifically to give 1-aza-7-oxabicyclo[2.2.1]heptanes whilst sterically unencumbered aryl aldoximes and 1,4-dienes give 1-aza-2-oxabicyclo[3.2

  醛酮肟和酮肟通过涉及N-烯基硝酮中间体的串联过程与一系列包含官能化的1,3-，1,4-和1,5-二烯的双官能Michael受体-双极性亲和底物反应。1,3-二烯在区域和立体上发生特异性反应，生成1-氮杂-7-氧杂双环[2.2.1]庚烷，而空间上不受阻碍的芳基醛肟和1,4-二烯生成1-氮杂-2-氧杂双环[3.2]。 1]辛烷衍生物。1-Aza-2-oxa-和1-aza-8-oxa-双环[3.2.1]辛烷的酮肟和1.4消旋混合物。1,5-二烯和酮肟与区域和立体特异性反应，生成1-aza-8-氧杂双环[3.2.1]辛烷衍生物，而苯甲醛肟则生成1：1异构体的1-aza-8-氧杂双环[3.2]混合物。 1]辛烷以及两个差向异构的1-氮杂-2-氧杂双环[3.2.1]辛烷。串联过程的区域和立体化学结果受双功能底物中连接链的长度和性质以及在过渡状态下肟和双极性亲核体上取代基之间的空间相互作用所控制。据报道1-氮杂-7-氧杂双环[2
• 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。
• Photocycloaddition of 2,5-dihydrothiophen SS-dioxides to α,β-unsaturated cyclic anhydrides. Synthesis of 10-hydroxygeraniol
  作者：John R. Williams、Charles Lin

  DOI：10.1039/c39810000752

  日期：——

  10-Hydroxygeraniol (6c) was synthesized from 2,5-dihydro-3-methythiophen SS-dioxide (1b) and citraconic anhydrid (2b) in 48% overall yield via irradiation followed by thermal extrusion of SO2 from the intermediate photoadduct (3b) and a Cope rearrangement of the resulting divinyl diester (5b).

  由2,5-二氢-3-甲基噻吩SS-二氧化物（1b）和柠康酸酐（2b）通过辐照，然后从中间光加合物（3b）热挤出SO 2合成10-羟基香叶醇（6c））和相应的二乙烯基二酯的应对重排（5b）。
• Tandem Olefin Metathesis/Oxidative Cyclization: Synthesis of Tetrahydrofuran Diols from Simple Olefins
  作者：Peter K. Dornan、Daniel Lee、Robert H. Grubbs

  DOI：10.1021/jacs.6b02653

  日期：2016.5.25

  A tandem olefin metathesis/oxidative cyclization has been developed to synthesize 2,5-disubstituted tetrahydrofuran (THF) diols in a stereocontrolled fashion from simple olefin precursors. The ruthenium metathesis catalyst is converted into an oxidation catalyst in the second step and is thus responsible for both catalytic steps. The stereochemistry of the 1,5-diene intermediate can be controlled through

  已经开发出串联烯烃复分解/氧化环化，以从简单的烯烃前体以立体控制的方式合成 2,5-二取代四氢呋喃 (THF) 二醇。钌复分解催化剂在第二步中转化为氧化催化剂，因此负责两个催化步骤。1,5-二烯中间体的立体化学可以通过选择催化剂和进行复分解的类型来控制。这种烯烃立体化学然后通过高度立体有择的氧化环化来控制 THF 二醇立体化学。