7,7-dimethoxyhept-1-ene | 28995-68-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7,7-dimethoxyhept-1-ene
• 英文别名: 7,7-dimethoxy-hept-1-ene；1,1-Dimethoxy-6-heptene
• CAS: 28995-68-8
• 化学式: C₉H₁₈O₂
• 分子量: 158.241
• InChiKey: MIXTVLOSKNHONV-UHFFFAOYSA-N

物化性质

• 沸点：
  50 °C(Press: 5 Torr)
• 密度：
  0.854±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  11
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  7,7-dimethoxyhept-1-ene 在 盐酸 、 正丁基锂 、 mercury(II) perchlorate 、 美雄醇 、 三乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 为溶剂， 反应 31.08h， 生成 methyl (1S,4S,8R,9S)-4-butoxy-5,7-dioxa-6-azatricyclo[7.4.0.01,6]tridecane-8-carboxylate
  参考文献：
  名称：

  Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions. 17. The Spiro Mode. Efficient and Highly Selective Synthesis of Azapropellanes

  摘要：

  A new variant of the tandem inter [4 + 2]/intra [3 + 2] nitroalkene cycloaddition has been developed. Intermolecular [4 + 2] cycloaddition of a 2-nitroalkene (bearing an unsaturated ester moiety, the dipolarophile) with a vinyl ether produces a cyclic nitronate substituted at C(3) wherein the only stereogenic center is the anomeric carbon C(6). Since the dipolarophile is attached to a tether extending from the C(3) of the nitronate (a-carbon of the nitroalkene), the intramolecular [3 + 2] cycloaddition affords a spiro tricyclic nitroso acetal. The cycloaddition proceeds smoothly for three- and four-atom tethers to afford five- and six-membered rings. Both E- and Z-unsaturated esters serve well as dipolarophiles, but the E-isomers react more selectively. Hydrogenolysis of the nitroso acetals affords the spiro tricyclic alpha-hydroxy lactams in good yield. Remarkably high levels of asymmetric induction are observed with the use of a chiral vinyl ether derived from (1R,2S)-2-phenylcyclohexanol. The origin of asymmetric induction is a combination of the established face selectivity of the enol ether and the preference for a distal fold of the tether away from the: substituent on the anomeric carbon. The scope and limitations of this transformation and an analysis of the origin of stereoselectivity are provided.

  DOI：

  10.1021/jo9719057
• 作为产物：
  描述：

  环己烯 在 正丁基锂 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 36.0h， 生成 7,7-dimethoxyhept-1-ene
  参考文献：
  名称：

  间苯二酸内酯新cosmosin A及其对映异构体的总合成

  摘要：

  已经建立了分配给最近报道的间苯二酸内酯（RAL）新cosmosin A的结构1的总合成。关键步骤包括烯烃交叉复分解，闭环复分解，钯催化的Meinwald重排和Mitsunobu酯化反应。反应顺序的后期和简单修饰也提供了化合物ent - 1，该化合物实际上代表了天然产物的真实结构。

  DOI：

  10.1021/acs.joc.5b00590

文献信息

• Total Syntheses of the Resorcylic Acid Lactone Neocosmosin A and Its Enantiomer
  作者：Yiwen Zhang、Michael Dlugosch、Martin Jübermann、Martin G. Banwell、Jas S. Ward

  DOI：10.1021/acs.joc.5b00590

  日期：2015.5.1

  A total synthesis of the structure, 1, assigned to the recently reported resorcylic acid lactone (RAL) neocosmosin A has been established. Olefin-cross metathesis, ring-closing metathesis, palladium-catalyzed Meinwald rearrangement, and Mitsunobu esterification reactions were used as key steps. A late-stage and simple modification to the reaction sequence also provided compound ent-1 that, in fact

  已经建立了分配给最近报道的间苯二酸内酯（RAL）新cosmosin A的结构1的总合成。关键步骤包括烯烃交叉复分解，闭环复分解，钯催化的Meinwald重排和Mitsunobu酯化反应。反应顺序的后期和简单修饰也提供了化合物ent - 1，该化合物实际上代表了天然产物的真实结构。
• Ozonolytic cleavage of cycloalkenes to terminally differentiated products
  作者：G. Cardinale、J.C. Grimmelikhuysen、J.A.M. Laan、J.P. Ward

  DOI：10.1016/s0040-4020(01)91144-5

  日期：1984.1
• Electroorganic chemistry. VII. Anodic oxidation of cyclopropanes
  作者：Tatsuya Shono、Yoshihiro Matsumura、Yukio Nakagawa

  DOI：10.1021/jo00812a011

  日期：1971.7
• CARDINALE, G.;GRIMMELIKHUYSEN, J. C.;LAAN, J. A. M.;WARD, J. P., TETRAHEDRON, 1984, 40, N 10, 1881-1883
  作者：CARDINALE, G.、GRIMMELIKHUYSEN, J. C.、LAAN, J. A. M.、WARD, J. P.

  DOI：——

  日期：——
• Organocatalytic Access to a <i>cis</i>-Cyclopentyl-γ-amino Acid: An Intriguing Model of Selectivity and Formation of a Stable 10/12-Helix from the Corresponding γ/α-Peptide
  作者：Rossana Fanelli、Dénes Berta、Tamás Földes、Edina Rosta、Robert Andrew Atkinson、Hans-Jörg Hofmann、Kenneth Shankland、Alexander J. A. Cobb

  DOI：10.1021/jacs.9b10861

  日期：2020.1.22

  In this study, we have developed a highly enantioselective organocatalytic route to the (1S,2R)-2-(aminomethyl)cyclopentane-1-carboxylic acid monomer precursor, which has a cis-configuration between the C- and N-termini around the cyclopentane core. Kinetic measurements show that the product distribution changes over time due to epimerization of the C1 center. Computations suggest the cis-selectivity is a result of selective C-C bond formation, while subsequent steps appear to influence the selectivity at higher temperature. The resulting gamma-amino acid residue was incorporated into a novel gamma/alpha-peptide, which forms a well-ordered 10/12-helix with alternate H-bond directionality in spite of the smallest value of the zeta-angle yet observed for a helix of this type. This highly defined structure is also a result of the narrow range of potential zeta-angles in our monomer. In contrast, the larger range of potential zeta-values observed for the corresponding trans-system can be fulfilled by several competing helical structures.