(3-phenylbicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3-phenylbicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone
• 英文别名: ((1S,2R,3R,4R)-3-phenylbicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone；[(1S,2R,3R,4R)-3-phenyl-2-bicyclo[2.2.1]hept-5-enyl]-pyridin-2-ylmethanone
• 化学式: C₁₉H₁₇NO
• 分子量: 275.35
• InChiKey: ITLBWWBLBQJKTH-BURFUSLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  30
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-(1-氧代吡啶-1-鎓-2-基)乙酮 在 Zn(II) triflate potassium tert-butylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 (3-phenylbicyclo[2.2.1]hept-5-en-2-yl)(pyridin-2-yl)methanone
  参考文献：
  名称：

  2-Alkenoyl Pyridine N-Oxides, Highly Efficient Dienophiles for the Enantioselective Cu(II)−Bis(oxazoline) Catalyzed Diels−Alder Reaction

  摘要：

  2-Alkenoyl pyridine N-oxides are introduced as a new kind of efficient dienophiles for the Cu(II)-bis(oxazoline) (BOX) catalyzed enantioselective Diels-Alder reaction affording higher reactivity and enantioselectivity (ee's up to 96%) than the corresponding nonoxidized 2-alkenoyl pyridines.

  DOI：

  10.1021/ol0705752

文献信息

• Construction of a hybrid biocatalyst containing a covalently-linked terpyridine metal complex within a cavity of aponitrobindin
  作者：Tomoki Himiyama、Daniel F. Sauer、Akira Onoda、Thomas P. Spaniol、Jun Okuda、Takashi Hayashi

  DOI：10.1016/j.jinorgbio.2015.12.026

  日期：2016.5

  Cu2 +-bound NB–1 is found to catalyze a Diels–Alder reaction between azachalcone and cyclopentadiene in 22% yield, which is higher than that of the Cu2 +–tpy complex without the NB matrix. The results suggest that the hydrophobic cavity close to the copper active site within the NB scaffold supports the binding of the two substrates, dienophile and diene, to promote the reaction.

  构建了一种杂化生物催化剂，该杂化生物催化剂在刚性β-桶蛋白硝基结合蛋白（NB）中包含金属联吡啶（tpy）配合物。具有马来酰亚胺基团的tpy配体N- [2-（[[2,2'：6'，2''-叔吡啶] -4'-酰氧基）乙基]马来酰亚胺（1）与腔体内的Cys96共价连接NB制备共轭NB- 1。紫外可见光谱和ESI-TOF MS测量证实了NB- 1中的tpy配体与Cu 2 +，Zn 2 +或Co 2 +离子结合。发现与Cu 2 +结合的NB– 1催化氮杂查尔酮与环戊二烯之间的Diels–Alder反应，收率为22％，高于Cu 2 +-tpy复杂，不包含NB矩阵。结果表明，靠近NB支架内铜活性位点的疏水腔可支持亲二烯体和二烯这两种底物的结合，从而促进反应。
• Artificial Metalloenzymes with the Neocarzinostatin Scaffold: Toward a Biocatalyst for the Diels-Alder Reaction
  作者：Wadih Ghattas、Lur Cotchico-Alonso、Jean-Didier Maréchal、Agathe Urvoas、Maëva Rousseau、Jean-Pierre Mahy、Rémy Ricoux

  DOI：10.1002/cbic.201500445

  日期：2016.3.2

  A new artificial enzyme formed by associating NCS‐3.24 with a copper complex catalyzed the Diels–Alder cyclization of cyclopentadiene with 2‐azachalcone and led to an increase in the formation of the exo‐products. Molecular modeling proposed the preferred relative positioning of both the Trojan horse complex and the two substrates.

  NCS-3.24与铜配合物形成的一种新的人造酶催化了环戊二烯与2-氮杂十二烷的狄尔斯-阿尔德环化反应，并增加了外产物的形成。分子建模提出了特洛伊木马复合体和两种底物的优选相对位置。
• Asymmetric Diels–Alder Reaction of α,β-Unsaturated Oxazolidin-2-one Derivatives Catalyzed by a Chiral Fe(III)-Bipyridine Diol Complex
  作者：Mao Li、Virginie Carreras、Angela Jalba、Thierry Ollevier

  DOI：10.1021/acs.orglett.7b03939

  日期：2018.2.16

  An asymmetric FeIII-bipyridine diol catalyzed Diels–Alder reaction of α,β-unsaturated oxazolidin-2-ones has been developed. Among various FeII/FeIII salts, Fe(ClO4)3·6H2O was selected as the Lewis acid of choice. The use of a low catalyst loading (2 mol % of Fe(ClO4)3·6H2O and 2.4 mol % of Bolm’s ligand) afforded high yields (up to 99%) and high enantiomeric excesses (up to 98%) of endo-cycloadducts

  已开发出一种不对称的Fe III-联吡啶二醇催化的α，β-不饱和恶唑烷-2-酮的Diels-Alder反应。在各种Fe II / Fe III盐中，选择Fe（ClO 4）3 ·6H 2 O作为选择的路易斯酸。使用低催化剂负载量（2 mol％的Fe（ClO 4）3 ·6H 2 O和2.4 mol％的Bolm配体）可获得高收率（最高99％）和高对映体过量（最高98％）。内在环戊二烯与取代的丙烯酰基恶唑烷丁二酮之间的狄尔斯-阿尔德反应的环加合物。其他非环状二烯导致对映选择性降低。提出的模型支持观察到的立体感应。
• An Efficient Cyclic Di-AMP Based Artificial Metalloribozyme for Enantioselective Diels-Alder Reactions
  作者：Qianqian Qi、Shuting Lv、Min Hao、Xingchen Dong、Youkun Gu、Peizhe Wu、Wenyue Zhang、Yashao Chen、Changhao Wang

  DOI：10.1002/ejoc.202000652

  日期：2020.8.2

  A small cyclic RNA of c‐di‐AMP and Cu2+ ions could assemble into an artificial metalloribozyme, that is able to catalyze the enantioselective Diels–Alder reactions with up to 80 % ee . The presence of c‐di‐AMP in the metalloribozyme not only achieves the chirality transfer but also gives rise to a significant rate enhancement.

  少量的c-di-AMP和Cu 2+离子环状RNA可以组装成人工金属核酶，该酶​​能够以高达80％ee的催化对映选择性Diels-Alder反应。金属核酶中c-di-AMP的存在不仅实现了手性转移，而且还大大提高了速率。
• Asymmetric Catalysis of Diels-Alder Cycloaddition of 2-Alkenoyl Pyridine with Cyclopentadiene by Binaphthol-Titanium Complex
  作者：Li Wang、Ji Zhang、Na Wang、Xin-Bin Yang、Qin Wang、Xiao-Qi Yu

  DOI：10.2174/157017809788681419

  日期：2009.7.1

  Asymmetric Diels-Alder reactions between aza-chalcone and cyclopentadiene (CP) catalyzed by the binaphthol-titanium (BINOL – Ti) in the presence of HMPA (80 mole %) were studied. The products were obtained with up to 87% ees.

  研究了在HMPA（80摩尔％）存在下联萘酚钛（BINOL-Ti）催化的氮杂查尔酮与环戊二烯（CP）之间的不对称Diels-Alder反应。获得的产品具有高达87％的ee。