6-oxo-hex-2-ynoic acid methyl ester | 79975-90-9

• 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: 6-oxo-hex-2-ynoic acid methyl ester
• 英文别名: methyl 6-oxo-2-hexynoate；methyl 6-oxohex-2-ynoate
• CAS: 79975-90-9
• 化学式: C₇H₈O₃
• 分子量: 140.139
• InChiKey: JRXXEUZUAXNTFJ-UHFFFAOYSA-N

物化性质

• 沸点：
  243.4±23.0 °C(Predicted)
• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-oxo-hex-2-ynoic acid methyl ester 在 草酰氯 、 sodium hydride 、 二甲基亚砜 、 三乙胺 、 magnesium bromide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.03h， 生成 methyl (5-butyl-furan-2-yl)acetate
  参考文献：
  名称：

  戊炔酮和己酮的阴离子环化：获得呋喃和吡喃衍生物

  摘要：

  在用碱处理时，戊炔酮 8a-f 发生所得烯醇化物与炔部分的阴离子加成反应，并以 10-91% 的产率提供 2,5-二取代呋喃 10a-f。所提出的机制涉及 2-亚甲基-二氢呋喃 11 作为中间体，其互变异构化产生观察到的产物。在α-甲基吡啶衍生物8g的情况下，可能形成烯醇化物12和13，随后分别转化为产物10g和14g。从己酮 9a-e 开始，发生类似的反应，以可比的产率形成吡喃衍生物 15 和 16。在相同的反应条件下，正丁基酮 9f 产生两种异构化合物，即 4H-吡喃 16f 和环己烯酮 17。

  DOI：

  10.1002/(sici)1099-0690(200002)2000:3<527::aid-ejoc527>3.0.co;2-n
• 作为产物：
  描述：

  2-(4-戊炔氧基)四氢-2H-吡喃 在 对甲苯磺酸 正丁基锂 、 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 6-oxo-hex-2-ynoic acid methyl ester
  参考文献：
  名称：

  电遥测：三和四取代烯烃的新方法。

  摘要：

  描述了一种新颖的电遥测方法，其中烷基或芳基碲酸根阴离子的迈克尔加成发生在活化的炔上，随后用质子以外的亲电子试剂（醛和酮）捕获乙烯基阴离子。该方法为三和四取代的烯烃提供了有效的区域和立体有择途径。研究了该化学方法学上的重要实例，其中在迈克尔反应中将芳基和烷基碲酸根阴离子添加到ω-酮炔基酯中，初始乙烯基阴离子被内部醛分子内捕获。反应中心被不同长度的烷基链束缚，以适度到良好的产率形成高度官能化的五，六，七和八元环。

  DOI：

  10.1021/jo0110146

文献信息

• The Intramolecular Allenolate Rauhut–Currier Reaction
  作者：James A. MacKay、Zachary C. Landis、Stephen E. Motika、Margaret H. Kench

  DOI：10.1021/jo3015769

  日期：2012.9.7

  intramolecular Rauhut–Currier reaction utilizing alkynoates as the initial conjugate acceptor affords densely functionalized 5- and 6-membered rings from ynoate-enoate, ynoate-enenitrile, and alkynyl sulfone-enenitrile substrates. Trialkylphosphines catalyze the reaction, and TMSCN serves as a pronucelophile to effect turnover of the catalyst and the formation of a second C–C bond. Because of the highly electrophilic

  利用炔酸酯作为初始共轭受体的分子内Rauhut-Currier反应提供了由炔酸酯-烯酸酯，炔酸酯-乙腈和炔基砜-乙腈底物稠密官能化的5和6元环。三烷基膦催化该反应，而TMSCN可作为亲核亲核试剂，以影响催化剂的周转率和第二个C–C键的形成。由于高度亲电的炔烃受体，该反应产生的产物无法从传统的Rauhut-Currier反应中轻易获得。
• Copper-Catalyzed Enantioselective Intramolecular Conjugate Addition/Trapping Reactions: Synthesis of Cyclic Compounds with Multichiral Centers
  作者：Kangying Li、Alexandre Alexakis

  DOI：10.1002/chem.200601327

  日期：2007.4.27

  The Cu-catalyzed enantioselective conjugate addition of dialkylzinc to bis-alpha,beta-unsaturated carbonyl compounds followed by the intramolecular trapping of the zinc enolate in the presence of chiral phosphoramidite ligands was investigated. Cyclic and heterocyclic compounds with multichiral centers were formed as a mixture of two diastereomers with excellent diastereoselectivities (up to 99:1)

  研究了铜催化的双烷基锌向双-α，β-不饱和羰基化合物的对映选择性共轭加成反应，然后在手性亚磷酰胺配体的存在下分子内捕获烯醇酸锌。具有多手性中心的环状和杂环化合物是两种非对映异构体的混合物，具有优异的非对映选择性（最高99：1）和对映选择性（最高94％ee，ee =对映体过量）。立体化学被确定为主要产品是反式，反式和次要产品是反式，顺式。通过与反式-3-壬烯-2-酮和Et（2）Zn衍生的类似加合物或通过将Me（2）Zn共轭加到反式-1-中获得的加合物进行比较，确定了环状化合物的绝对构型苯基-非-2-en-1-一个。
• The use of furanyl titanium compounds for the synthesis of 2,4-substituted furans
  作者：Helga Haarmann、Wolfgang Eberbach

  DOI：10.1016/s0040-4039(00)92116-6

  日期：1991.2

  The metal derivatives 2-5, derived from the protected 4-bromo-2-furancarbaldehydes 1a,b, were reacted with the bifunctional reagent 6 bearing an aldehyde and an ester function. Whereas the Li-, Mg- and Zn-species turned out to be either unselective and/or too unreactive, the Ti-derivatives 5a,b gave the addition products 7a,b in good yield and with high chemoselectivity.

  使衍生自受保护的4-溴-2-呋喃甲醛1a，b的金属衍生物2-5与带有醛和酯官能团的双官能试剂6反应。Li，Mg和Zn种类要么是非选择性的和/或太不活泼的，而Ti衍生物5a，b则以高收率和高化学选择性提供了加成产物7a，b。
• A Domino Diels–Alder Approach toward the Tetracyclic Nicandrenone Framework
  作者：Emily G. Mackay、Marck Nörret、Leon S.-M. Wong、Ignace Louis、Andrew L. Lawrence、Anthony C. Willis、Michael S. Sherburn

  DOI：10.1021/acs.orglett.5b02412

  日期：2015.11.20

  The tetracarbocyclic framework of the nicandrenone natural products is formed in one step from a linear precursor via a domino intramolecular Diels-Alder/intramolecular furan Diels-Alder/aromatization sequence. The approach represents a new 0 -> ABCD strategy for the preparation of aromatic steroids.
• Diastereoselective cycloisomerizations of enediynes via palladium catalysis
  作者：Barry M. Trost、Yian Shi

  DOI：10.1021/ja00079a033

  日期：1993.12

  Considerations of atom economy drive a search for reactions that are simple additions which, performed intramolecularly, are cycloisomerizations. Exposure of acyclic enediynes to a catalyst generated by mixing a Pd(O) complex with acetic acid normally in the presence of a phosphine ligand creates [5.6.51 and [6.6.51 tricycles with extraordinary diastereoselectivity of remote stereogenic centers. Effects of substituents on the tethers as well as the olefinic and acetylenic bonds reveal a wide tolerance of functionality. While geminal substitution facilitates the cycloisomerization, it is not required. Allylic oxygen plays a role as a regioselectivity control element. Cycloisomerization dominates over allylic ionization in such cases by proper tuning of the ligand. The mechanism of this reaction appears to vary depending upon the structure of the substrate. In the normal cases, the process involves three stages, initiation, propagation, and termination. Chemoselective initiation at the acetylenic linkage closest to one of the chain's termini occurs by hydropalladation. Propagation entails intramolecular carbametalations. Termination by beta-hydrogen elimination generates a hexatriene that undergoes high rotoselectivity in its disrotatory cyclization to generate the final product. Blocking formation of the hexatriene shuts down reaction. With substrates bearing a gamma-siloxypropiolate as the acetylenic initiator, cycloisomerization forms a tricycle with different positions of the double bonds. In contrast' to the case of the other substrates, blocking formation of a hexatriene does not shut down cycloisomerization. Invoking a novel intramolecular Diels-Alder reaction of a dienylpalladium intermediate derived from the diyne moiety with the olefin, likely assisted by coordination to palladium, accounts for our observations. The ease of availability of the acyclic substrates because of the versatility of the acetylenes combined with the high chemo-, regio-, and diastereoselectivity makes this atom-economical reaction a very practical approach for the construction of polycycles.