1'-Benzyl-7'-methylspiro[cyclohexane-1,2'-pyrano[4,3-b]pyridine]-5'-one | 234774-83-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1'-Benzyl-7'-methylspiro[cyclohexane-1,2'-pyrano[4,3-b]pyridine]-5'-one
• 英文别名: 1'-benzyl-7'-methylspiro[cyclohexane-1,2'-pyrano[4,3-b]pyridine]-5'-one
• CAS: 234774-83-5
• 化学式: C₂₁H₂₃NO₂
• 分子量: 321.419
• InChiKey: CRLAHJCSRNPPIE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  丁炔二酸二甲酯 、 1'-Benzyl-7'-methylspiro[cyclohexane-1,2'-pyrano[4,3-b]pyridine]-5'-one 以 甲苯 为溶剂， 反应 24.0h， 以50%的产率得到3-Methyl-1-oxo-1H-isochromene-5,6-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  A Formal [3 + 3] Cycloaddition Reaction. Improved Reactivity Using α,β-Unsaturated Iminium Salts and Evidence for Reversibility of 6π-Electron Electrocyclic Ring Closure of 1-Oxatrienes

  摘要：

  A detailed account regarding a formal [3 + 3] cycloaddition method using 4-hydroxy-2-pyrones and 1,3-diketones is described here. This formal cycloaddition reaction or annulation reaction is synthetically useful for constructing 2H-pyranyl heterocycles. The usage of alpha,beta-unsaturated iminium salts is significant in controlling competing reaction pathways to give exclusively 2H-pyrans. Most significantly, experimental evidence is provided to support the mechanism of this reaction that involves a sequential Knoevenagel condensation and a reversible 6pi-electron electrocyclic ringclosure of 1-oxatrienes.

  DOI：

  10.1021/jo020688t
• 作为产物：
  描述：

  6-methyl-4-(benzylamino)-2-pyrone 、 环己基亚基乙醛 在 哌啶 、 乙酸酐 作用下， 以 乙酸乙酯 、 甲苯 为溶剂， 反应 25.08h， 以81%的产率得到1'-Benzyl-7'-methylspiro[cyclohexane-1,2'-pyrano[4,3-b]pyridine]-5'-one
  参考文献：
  名称：

  Formal Cycloaddition Reactions of Vinylogous Amides with α,β-Unsaturated Iminiums. A Strategy for Constructing Piperidinyl Heterocycles

  摘要：

  A formal [3 + 3] cycloaddition strategy for constructing piperidinyl heterocycles from vinylogous amides and alpha,beta-unsaturated iminiums is described here, These reactions proceed well, leading to various heterocycles that could serve as useful synthetic building blocks. Comparative studies between the reactivities of vinylogous amides and other 1,3-diketo systems have also been examined. Preferences for the nitrogen atom during the electrocyclic ring closure step are noted in these reactions, and preliminary calculations suggest that these preferences could result from electronic factors.

  DOI：

  10.1021/ol990107v

文献信息

• Stereoselective Formal [3 + 3] Cycloaddition Approach to <i>cis-</i>1-Azadecalins and Synthesis of (−)-4<i>a</i>,8<i>a</i>-<i>diepi</i>-Pumiliotoxin C. Evidence for the First Highly Stereoselective 6π-Electron Electrocyclic Ring Closures of 1-Azatrienes
  作者：Heather M. Sklenicka、Richard P. Hsung、Michael J. McLaughlin、Lin-li Wei、Aleksey I. Gerasyuto、William B. Brennessel

  DOI：10.1021/ja020698b

  日期：2002.9.1

  Evidence is described here to support that a highly stereoselective 6pi-electron electrocyclic ring closure of 1-azatrienes is a key step in formal [3 + 3] cycloaddition or annulation reactions of chiral vinylogous amides with alpha,beta-unsaturated iminium salts. This would represent the first highly stereoselective 6pi-electron electrocyclic ring closure of 1-azatrienes. We have also unambiguously

  此处描述的证据支持 1-氮杂三烯的高度立体选择性 6pi 电子电环闭合是手性乙烯基酰胺与 α,β-不饱和亚胺盐正式 [3 + 3] 环加成或环化反应的关键步骤。这将代表 1-氮杂三烯的第一个高度立体选择性的 6pi 电子电环闭合。我们还明确地证明了这些特定的闭环是可逆的，导致主要的非对映异构体在热力学上也更稳定，并且旋转偏好也可能起作用。此处说明了合成应用，以立体选择性地将所得二氢吡啶转化为在 C2 和 C2a 处具有独特反相对立体化学的顺式 1-氮杂萘烷，从而合成 (-)-pumiliotoxin C 的表观异构体。
• A Formal [3 + 3] Cycloaddition Reaction. Improved Reactivity Using α,β-Unsaturated Iminium Salts and Evidence for Reversibility of 6π-Electron Electrocyclic Ring Closure of 1-Oxatrienes
  作者：Hong C. Shen、Jiashi Wang、Kevin P. Cole、Michael J. McLaughlin、Christopher D. Morgan、Christopher J. Douglas、Richard P. Hsung、Heather A. Coverdale、Aleksey I. Gerasyuto、Juliet M. Hahn、Jia Liu、Heather M. Sklenicka、Lin-Li Wei、Luke R. Zehnder、Craig A. Zificsak

  DOI：10.1021/jo020688t

  日期：2003.3.1

  A detailed account regarding a formal [3 + 3] cycloaddition method using 4-hydroxy-2-pyrones and 1,3-diketones is described here. This formal cycloaddition reaction or annulation reaction is synthetically useful for constructing 2H-pyranyl heterocycles. The usage of alpha,beta-unsaturated iminium salts is significant in controlling competing reaction pathways to give exclusively 2H-pyrans. Most significantly, experimental evidence is provided to support the mechanism of this reaction that involves a sequential Knoevenagel condensation and a reversible 6pi-electron electrocyclic ringclosure of 1-oxatrienes.
• Formal Cycloaddition Reactions of Vinylogous Amides with α,β-Unsaturated Iminiums. A Strategy for Constructing Piperidinyl Heterocycles
  作者：Richard P. Hsung、Lin-Li Wei、Heather M. Sklenicka、Christopher J. Douglas、Michael J. McLaughlin、Jason A. Mulder、Letitia J. Yao

  DOI：10.1021/ol990107v

  日期：1999.8.1

  A formal [3 + 3] cycloaddition strategy for constructing piperidinyl heterocycles from vinylogous amides and alpha,beta-unsaturated iminiums is described here, These reactions proceed well, leading to various heterocycles that could serve as useful synthetic building blocks. Comparative studies between the reactivities of vinylogous amides and other 1,3-diketo systems have also been examined. Preferences for the nitrogen atom during the electrocyclic ring closure step are noted in these reactions, and preliminary calculations suggest that these preferences could result from electronic factors.