dodec-2-yn-1-al | 71250-13-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dodec-2-yn-1-al
• 英文别名: dodec-2-ynal
• CAS: 71250-13-0
• 化学式: C₁₂H₂₀O
• 分子量: 180.29
• InChiKey: RBQZWFLEHANRSH-UHFFFAOYSA-N

物化性质

• 熔点：
  7°C (estimate)
• 沸点：
  303.13°C (estimate)
• 密度：
  0.8879 (estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  dodec-2-yn-1-al 在 喹啉 、 盐酸 、 sodium tetrahydroborate 、 正丁基锂 、 氢气 、 magnesium sulfate 、 二异丙胺 作用下， 以 四氢呋喃 、 甲醇 、 正庚烷 、 水 、 乙酸乙酯 为溶剂， 反应 12.58h， 生成 (2S)-3-(((6E,8Z)-5-hydroxyoctadeca-6,8-dien-1-yl)oxy)propane-1,2-diol
  参考文献：
  名称：

  从 Calcarean 海绵 Pericharax heteroraphis 分离、合成和绝对构型 Pericharaxins A 和 B、差向异构羟基多烯甘油醚

  摘要：

  从钙质海绵Pericharax heteroraphis中分离出天然存在的差向异构羟基多烯甘油醚 pericharaxins A ( 1a ) 和 B ( 1b ) 。在光谱数据分析和七步全合成的基础上，建立了两种非对映异构体的结构和立体化学表征。Pericharaxins A ( 1a ) 和 B ( 1b ) 的混合物) 通过合成和天然样品的手性相 HPLC 分析证明是差向异构体。差向异构体的进一步分离和 Mosher 方法对合成化合物的应用允许明确的绝对构型分配。虽然天然产物和合成中间体显示对 HCT116 细胞系无细胞毒性，但在 ATDC5 细胞中使用人 X 型胶原转录活性的软骨内分化活性是有趣的。

  DOI：

  10.3390/md20100635
• 作为产物：
  描述：

  1-tetrahydropyranyloxy-n-2-dodecyn 在 manganese(IV) oxide 、 ion-exchange resin Dowx-50w 作用下， 以 甲醇 、 正己烷 为溶剂， 反应 14.3h， 生成 dodec-2-yn-1-al
  参考文献：
  名称：

  A new aldol condensation of .alpha.-allenic esters with aldehydes, including a one-pot synthesis of enyne compounds

  摘要：

  DABCO-catalyzed condensations of ethyl 2,3-butadienoate (1a) with aldehydes at -6 to 25-degrees-C gave 3-hydroxy-2-vinylidenealkanoates 3 in 41-54% yields. Butyllithium-promoted condensations of 1a with aldehydes at -105 to -70-degrees-C afforded 3 in 56-67% yields. Reaction of ethyl 2,3-hexadienoate (1k) with 1-heptanal in the presence of butyllithium gave ethyl 3-hydroxy-2-(1-butenylidene)nonanoate (3k) in 64 % yield; however, when the butyllithium-promoted condensation of 1k with aldehydes was carried out at -90 to -70-degrees-C and then treated in the same pot with wet THF for 11-27 h at room temperature, ethyl (E)-2-(1-alkynyl)-2-alkenoates 7 (12-36% yields) were obtained along with 3 (14-26% yields).

  DOI：

  10.1021/jo00074a020

文献信息

• Catalytic Asymmetric Direct Henry Reaction of Ynals: Short Syntheses of (2S,3R)-(+)-Xestoaminol C and (−)-Codonopsinines
  作者：Daisuke Uraguchi、Shinji Nakamura、Takashi Ooi

  DOI：10.1002/anie.201004072

  日期：——

  Triple for all: Various optically active anti‐β‐nitro propargylic alcohols are synthesized by the catalytic stereoselective addition of nitroalkanes to ynals (the direct Henry reaction of ynals). The utilization of the rich chemistry of carbon–carbon triple bond allows rapid access to three natural products.

  对于所有人而言，都是三重：通过将硝基烷烃催化立体选择性地加成到醛缩醛上（醛缩醛的直接亨利反应），合成了各种旋光性的抗β-硝基炔丙醇。利用碳-碳三键的丰富化学成分，可以快速获得三种天然产物。
• Stereoselective Synthesis of (+)-Nephrosteranic Acid, (+)-trans-Cognac Lactone, and (+)-trans-Whisky Lactone using a Chiral Cyclohexadienyl Ti Compound
  作者：Florian Schleth、Thomas Vogler、Klaus Harms、Armido Studer

  DOI：10.1002/chem.200400237

  日期：2004.9.6

  3-dioxolandimethanol) cyclohexadienyl Ti derivative with various aldehydes led to the corresponding homoallylic alcohols with excellent diastereo- and enantioselectivities. Lower selectivities were obtained with chiral B-cyclohexadienyldiisopinocampheylborane. The 1,3-cyclohexadienes are very useful building blocks for the preparation of biologically important gamma-butyrolactones. Short efficient syntheses of (+)-nephrosteranic

  我们提出了环己二烯从3金属1，4-环己二烯到各种醛的立体选择性转移。路易斯酸介导的醛的“烯丙基化”通过3-甲硅烷基化和3-苯乙烯基化的1，4-环己二烯的处理不能以高非对映选择性实现。相反，环己二烯基钛化合物与脂族和芳族醛的反应均具有优异的非对映选择性。手性TADDOL衍生的（TADDOL，2,2-二甲基-α，α，α'，α'-四苯基-1,3-二氧代兰二甲醇）环己二烯基Ti衍生物与各种醛的反应导致相应的均丁醇具有出色的非对映体和对映选择性。用手性B-环己二烯基二异硫代樟脑硼烷获得较低的选择性。1 3-环己二烯是制备生物学上重要的γ-丁内酯的非常有用的结构单元。描述了通过1，4-环己二烯的不对称化来短效地合成（+）-肾甾酸，（+）-反式威士忌内酯和（+）-反白兰地内酯。
• Amplification of chirality by transition metal coordination: synthesis of chiral allenes and allene manganese complexes of high enantiomeric purity. Synthesis of methyl ( R , E )-(−)-(2,4,5-tetradecatrienoate (pheromone of Acanthoscelides obtectus (say))
  作者：Michel Franck-Neumann、Daniel Martina、Denis Neff

  DOI：10.1016/s0957-4166(98)00023-8

  日期：1998.2

  The enhancement of the asymmetry of chiral allenes by coordination with a transition metal can be turned to account for (easy) resolution of the complexes and therefore the allenes themselves. This is illustrated here on allene aldehyde complexes of (eta-methylcyclopentadienyl) dicarbonylmanganese, possibly bearing a second electron withdrawing substituent, and by the synthesis of an optically active alkenylallenic insect pheromone of high enantiomeric purity. (C) 1998 Elsevier Science Ltd. All rights reserved.
• A new aldol condensation of .alpha.-allenic esters with aldehydes, including a one-pot synthesis of enyne compounds
  作者：Sadao Tsuboi、Hirofumi Kuroda、Satoshi Takatsuka、Takashi Fukawa、Takashi Sakai、Masanori Utaka

  DOI：10.1021/jo00074a020

  日期：1993.10

  DABCO-catalyzed condensations of ethyl 2,3-butadienoate (1a) with aldehydes at -6 to 25-degrees-C gave 3-hydroxy-2-vinylidenealkanoates 3 in 41-54% yields. Butyllithium-promoted condensations of 1a with aldehydes at -105 to -70-degrees-C afforded 3 in 56-67% yields. Reaction of ethyl 2,3-hexadienoate (1k) with 1-heptanal in the presence of butyllithium gave ethyl 3-hydroxy-2-(1-butenylidene)nonanoate (3k) in 64 % yield; however, when the butyllithium-promoted condensation of 1k with aldehydes was carried out at -90 to -70-degrees-C and then treated in the same pot with wet THF for 11-27 h at room temperature, ethyl (E)-2-(1-alkynyl)-2-alkenoates 7 (12-36% yields) were obtained along with 3 (14-26% yields).
• Isolation, Synthesis and Absolute Configuration of the Pericharaxins A and B, Epimeric Hydroxy-Polyene Glycerol Ethers from the Calcarean Sponge Pericharax heteroraphis
  作者：Capucine Jourdain de Muizon、Céline Moriou、Sylvain Petek、Merrick Ekins、Marthe Rousseau、Ali Al Mourabit

  DOI：10.3390/md20100635

  日期：——

  epimeric hydroxy-polyene glycerol ether pericharaxins A (1a) and B (1b) were isolated from the calcarean sponge Pericharax heteroraphis. The structural and stereochemical characterization of both diastereoisomers were established on the basis of spectroscopic data analysis and total synthesis in seven steps. The mixture of pericharaxins A (1a) and B (1b) was proven to be epimeric by chiral-phase HPLC analysis

  从钙质海绵Pericharax heteroraphis中分离出天然存在的差向异构羟基多烯甘油醚 pericharaxins A ( 1a ) 和 B ( 1b ) 。在光谱数据分析和七步全合成的基础上，建立了两种非对映异构体的结构和立体化学表征。Pericharaxins A ( 1a ) 和 B ( 1b ) 的混合物) 通过合成和天然样品的手性相 HPLC 分析证明是差向异构体。差向异构体的进一步分离和 Mosher 方法对合成化合物的应用允许明确的绝对构型分配。虽然天然产物和合成中间体显示对 HCT116 细胞系无细胞毒性，但在 ATDC5 细胞中使用人 X 型胶原转录活性的软骨内分化活性是有趣的。