(R)-methyl 6-methyl-2-oxo-4-phenyl-3,4-dihydro-2H-pyran-5-carboxylate | 1313870-26-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (R)-methyl 6-methyl-2-oxo-4-phenyl-3,4-dihydro-2H-pyran-5-carboxylate
• 英文别名: methyl (R)-6-methyl-2-oxo-4-phenyl-3,4-dihydro-2H-pyran-5-carboxylate；methyl (4R)-6-methyl-2-oxo-4-phenyl-3,4-dihydropyran-5-carboxylate
• CAS: 1313870-26-6
• 化学式: C₁₄H₁₄O₄
• 分子量: 246.263
• InChiKey: ALZUZVYILFXHAF-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  乙酰乙酸甲酯 、 肉桂醛 在 三乙烯二胺 、 (5aR,10bS)-5a,10b-dihydro-2-(2,4,6-trimethylphenyl)-4H,6H-indeno[2,1-b]-1,2,4-triazolo[4,3-d]-1,4-oxazinium chloride 、 lithium chloride 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以81%的产率得到(R)-methyl 6-methyl-2-oxo-4-phenyl-3,4-dihydro-2H-pyran-5-carboxylate
  参考文献：
  名称：

  N-杂环卡宾/路易斯酸催化1，，3-二羰基化合物对α，β-不饱和醛的对映选择性好氧环化

  摘要：

  已经开发了通过氧化NHC催化的肉桂醛和1,3-二羰基化合物的新型高效需氧不对称环化反应，它可以以高收率和良好的对映选择性选择性合成各种对映体富集的二氢吡喃酮衍生物。具有脂肪族和芳香族取代基的各种α，β-不饱和醛和1,3-二羰基化合物具有良好的耐受性。空气直接用作氧化剂，以高效，廉价和绿色的方式进行了这种不对称环化反应。

  DOI：

  10.1021/acs.joc.6b01152

文献信息

• Chiral N-heterocyclic carbene catalyzed annulation of α,β-unsaturated aldehydes with 1,3-dicarbonyls
  作者：Zhi-Qiang Zhu、Xing-Liang Zheng、Ning-Fei Jiang、Xiaolong Wan、Ji-Chang Xiao

  DOI：10.1039/c1cc12778k

  日期：——

  Chiral N-heterocyclic carbene catalyzed annulations of ynals and enals with 1,3-dicarbonyls have been described. The two reactions provided direct and efficient methods for enantioselective synthesis of functionalized dihydropyranones. Comparatively, the reactions starting from ynals were atom-economical; furthermore the reactions of enals demonstrated broader substrate compatibility.

  已经描述了手性N-杂环卡宾催化的具有1，3-二羰基的烯醛和烯醛的环。这两个反应为功能化二氢吡喃酮的对映选择性合成提供了直接和有效的方法。相比之下，从自醛开始的反应是原子经济的。此外，烯醛的反应证明了更广泛的底物相容性。
• Enantioselective<i>N</i>-Heterocyclic Carbene-Catalyzed Michael Addition to α,β-Unsaturated Aldehydes by Redox Oxidation
  作者：Zi-Qiang Rong、Min-Qiang Jia、Shu-Li You

  DOI：10.1021/ol201595f

  日期：2011.8.5

  Enantioselective N-heterocyclic carbene-catalyzed Michael addition reactions to α,β-unsaturated aldehydes by redox oxidation were realized. With 10 mol % of camphor-derived triazolium salt D, 15 mol % of DBU, 5 mol % of NaBF4, and 100 mol % of quinone oxidant, the reactions of various dicarbonyl compounds with α,β-unsaturated aldehydes led to 3,4-dihydro-α-pyrones in good yields and excellent ee’s

  对映选择性Ñ -杂环卡宾催化迈克尔加成反应的α，通过氧化还原氧化β不饱和醛分别实现。用10摩尔％的樟脑衍生的三唑盐D，15摩尔％的DBU，5摩尔％的NaBF 4和100摩尔％的醌氧化剂，各种二羰基化合物与α，β-不饱和醛的反应导致3， 4-二氢-α-吡喃酮，收率高，ee优良。
• Direct β-Activation of Saturated Aldehydes to Formal Michael Acceptors through Oxidative NHC Catalysis
  作者：Junming Mo、Liang Shen、Yonggui Robin Chi

  DOI：10.1002/anie.201302152

  日期：2013.8.12

  mediated by N‐heterocyclic carbenes (NHCs) enables the direct β‐carbon functionalization of saturated aldehydes (see scheme). The reaction proceeds through two sequential oxidative steps to generate α,β‐unsaturated triazolium ester equivalents as formal Michael acceptors, which react with 1,3‐diketones and β‐ketone esters in an enantioselective manner.

  不走弯路：由N-杂环卡宾（NHC）介导的氧化催化作用可实现饱和醛的直接β-碳官能化（请参阅方案）。该反应通过两个连续的氧化步骤进行，以生成α，β-不饱和三唑鎓酯当量形式的Michael受体，它们与1,3-二酮和β-酮​​酯以对映选择性的方式反应。
• Direct Activation of β-sp³-Carbons of Saturated Carboxylic Esters as Electrophilic Carbons via Oxidative Carbene Catalysis
  作者：Bin Liu、Weihong Wang、Ruoyan Huang、Jiekuan Yan、Jichang Wu、Wei Xue、Song Yang、Zhichao Jin、Yonggui Robin Chi

  DOI：10.1021/acs.orglett.7b03650

  日期：2018.1.5

  An N-heterocyclic carbene-catalyzed oxidative LUMO activation of the β-cabons of saturated carboxylic esters is disclosed. This approach allows for efficient asymmetric access to lactams and lactones by directly installing functional groups to the typically inert β-sp3 carbons of saturated esters. The use of HOBt as an additive was found to significantly improve both yields and enantioselectivities

  公开了一种N-杂环卡宾催化的饱和羧酸酯的β-碳的氧化LUMO活化。该方法允许通过直接安装的官能团的典型惰性β-SP高效不对称获得内酰胺和内酯3个饱和酯的碳。发现使用HOBt作为添加剂可显着提高反应的产率和对映选择性。
• Oxidative NHC catalysis: direct activation of β sp³ carbons of saturated acid chlorides
  作者：Shi-Ya Zhu、Hua Zhang、Qing-Wei Ma、Dou Liu、Xin-Ping Hui

  DOI：10.1039/c8cc08578a

  日期：——

  activation of saturated acid chlorides by oxidative N-heterocyclic carbene catalysis has been successfully utilized to synthesize enantio-enriched spirooxindole lactones and δ-lactones. The reaction involves the transformation of the β sp3 carbon of saturated acid chlorides into an electrophilic carbon as a key step. The product was obtained in excellent yield and stereoselectivity.

  已成功利用氧化N-杂环卡宾催化对饱和酰氯的首次活化，来合成对映体富集的螺并吲哚内酯和δ-内酯。该反应涉及将饱和酰氯的βsp 3碳转化为亲电子碳的关键步骤。以优异的产率和立体选择性获得产物。