2-(4-bromophenyl)-2,3-dihydro-4H-pyran-4-one | 387388-81-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2-(4-bromophenyl)-2,3-dihydro-4H-pyran-4-one
• 英文别名: 2-(4-Bromophenyl)-2,3-dihydropyran-4-one
• CAS: 387388-81-0
• 化学式: C₁₁H₉BrO₂
• 分子量: 253.095
• InChiKey: MPEGIABUNUFOLD-UHFFFAOYSA-N

物化性质

• 沸点：
  338.1±41.0 °C(Predicted)
• 密度：
  1.509±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(4-bromophenyl)-2,3-dihydro-4H-pyran-4-one 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 cerium(III) chloride heptahydrate 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 2-(4-bromophenyl)-3,4-dihydro-2H-pyran-4-yl 3-oxobutanoate
  参考文献：
  名称：

  通过钯催化的脱羧烯丙基化可轻松获得顺式2,6-二取代的四氢吡喃：（±）-环草碱和（+）-去细胞肽A和B的总合成

  摘要：

  顺式-2,6-四氢吡喃是生物活性天然产物的重要结构骨架。顺式-2,6-二取代-3,6-二氢吡喃前体作为顺式-2,6-四氢吡喃前体的简便合成方法具有很高的区域选择性和立体选择性，且收率很高。该反应涉及各种3,4-dihydro-2 H-吡喃底物的钯催化脱羧烯丙基化。将此反应扩展至1,2-不饱和碳水化合物可实现具有挑战性的β-C-糖基化。基于此方法，只需简单的步骤即可完成（±）-中心叶lob碱和（+）-去细胞肽A和B的总合成。

  DOI：

  10.1002/chem.201303328
• 作为产物：
  描述：

  (E)-5-(4-Bromo-phenyl)-1-methoxy-5-trimethylsilanyloxy-pent-1-en-3-one 在 三氟乙酸 作用下， 生成 2-(4-bromophenyl)-2,3-dihydro-4H-pyran-4-one
  参考文献：
  名称：

  Nafion-H-catalyzed Mukaiyama aldol condensations and hetero Diels–Alder reactions using aldehydes and imines. Part 15: General synthetic methods

  摘要：

  Nafion-H catalyzes the Mukaiyama aldol condensation between aromatic aldehydes and the Danishefsky diene whereas the corresponding imines directly undergo hetero Diels-Alder cyclization to form 2,3-dihydro-gamma -pyridones. Some chiral acetal derived aldehydes were round to undergo Mukaiyama aldol condensation in the presence of Lewis acids but not with Nafion-H. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01592-1

文献信息

• 3,3‘-Br₂-BINOL-Zn Complex:  A Highly Efficient Catalyst for the Enantioselective Hetero-Diels−Alder Reaction
  作者：Haifeng Du、Jiang Long、Jieyu Hu、Xin Li、Kuiling Ding

  DOI：10.1021/ol027034r

  日期：2002.11.1

  [reaction: see text] A BINOLate-zinc complex prepared in situ from Et(2)Zn and 3,3'-dibromo-1,1'-bi-2-naphthol (3,3'-Br(2)-BINOL) was found to be a highly efficient catalyst for the enantioselective hetero-Diels-Alder reaction of Danishefsky's diene and aldehydes to give 2-substituted 2,3-dihydro-4H-pyran-4-one in up to quantitative yield and 98% ee.

  [反应：参见正文]由Et（2）Zn和3,3'-dibromo-1,1'-bi-2-naththol（3,3'-Br（2）-BINOL原位制备的BINOLate-锌复合物）被发现是Danishefsky's二烯和醛对映选择性杂Diels-Alder反应的高效催化剂，可得到定量最高收率和98％ee的2-取代的2,3-二氢-4H-吡喃-4-酮。
• Novel Cerium(III)–(<i>R</i>)-BNP Complex as a Storable Chiral Lewis Acid Catalyst for the Enantioselective Hetero-Diels–Alder Reaction
  作者：Tetsuji Hayano、Toshiaki Sakaguchi、Hiroshi Furuno、Masaaki Ohba、Hisashi Okawa、Junji Inanaga

  DOI：10.1246/cl.2003.608

  日期：2003.7

  A novel Ce(III)–(R)-BNP complex was conveniently prepared from CAN and (R)-BNP–Na, then successfully used as a homogeneous catalyst for the asymmetric hetero-Diels–Alder reaction affording, after acidic work-up, 6-substituted 5,6-dihydro-4H-pyran-4-one derivatives with high enantioselectivities (up to 94% ee). A mechanistically interesting positive nonlinear effect was also observed.

  一种新型的 Ce(III)-(R)-BNP 复合物由 CAN 和 (R)-BNP-Na 方便地制备，然后成功用作不对称杂-Diels-Alder 反应的均相催化剂，经过酸处理后, 6-取代的 5,6-dihydro-4H-pyran-4-one 衍生物，具有高对映选择性（高达 94% ee）。还观察到机械上有趣的正非线性效应。
• Palladium(<scp>ii</scp>)-catalyzed direct alkenylation of dihydropyranones
  作者：Shanshan Chen、Xihao Chang、Yu Tao、Haoming Chen、Yong Xia

  DOI：10.1039/c5ob00432b

  日期：——

  A palladium(ii)-catalyzed direct alkenylation reaction of dihydropyranones was developed.

  开发了一种钯催化的直接烯丙基化反应，用于二氢吡喃酮。
• Discovery of Exceptionally Efficient Catalysts for Solvent-Free Enantioselective Hetero-Diels−Alder Reaction
  作者：Jiang Long、Jieyu Hu、Xiaoqiang Shen、Baoming Ji、Kuiling Ding

  DOI：10.1021/ja0172518

  日期：2002.1.1

  Combinatorial coordination chemistry strategy combined with high-throughput screening techniques has been successfully applied to engineering practical enantioselective catalysts for asymmetric hetero-Diels-Alder reaction. The reaction of Danishefsky's diene with a variety of aldehydes can be carried out with 0.1-0.005 mol % of H4-BINOL/Ti/H4-BINOL or H4-BINOL/Ti/H8-BINOL catalysts at room temperature under solvent- and MS-free conditions to afford dihydropyrone derivatives with up to quantitative yield and 99.8% ee.
• Dramatically Synergetic Effect of Carboxylic Acid Additive on Tridentate Titanium Catalyzed Enantioselective Hetero-Diels–Alder Reaction: Additive Acceleration and Nonlinear Effect
  作者：Yu Yuan、Jiang Long、Jie Sun、Kuiling Ding

  DOI：10.1002/1521-3765(20021104)8:21<5033::aid-chem5033>3.0.co;2-t

  日期：2002.11.4

  This paper describes the successful development of a group of highly, efficient chiral tridentate titanium catalysts for hetero-Diels - Alder reaction of Danishefsky's diene and a variety of aldehydes through ligand and additive diversity. Dramatically synergetic effect of carboxylic acid additives and influence of substituent in chiral Schiff base ligands on the enantioselectivities of the reaction are reported. It was found that a chiral drug Naproxen (A21) was a highly efficient additive for Ti-catalyzed HDA reaction, affording 2-substituted 2,3-dihydro-4H-pyran-4-one in up to 97% ee and > 99% yields. Quantitative study of the effect of chiral carboxylic acid A21 revealed that the reaction could be accelerated by one order of magnitude. Another interesting feature of present catalytic system is the existence of significant positive nonlinear effect. which indicates that the heterochiral Schiff base-titanium complexes may have higher stability than their homochiral counterparts. As a result. the homochiral Schiff base - titanium complexes with higher ee than that of starting ligand will react with carboxylic acid additive to form the more active species and predominate the catalytic process. The isolation and characterization of stable heterochiral ((+/-)-L1)(2)Ti complex has also been successful, which strongly supported the explanation for positive nonlinear effect observed in the catalytic system.