(1S,2R,3R,4R)-2-(2-hydroxy-2-methylpropanoyl)-3-phenylbicyclo[2.2.1]hept-5-ene | 637033-21-7

• 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: (1S,2R,3R,4R)-2-(2-hydroxy-2-methylpropanoyl)-3-phenylbicyclo[2.2.1]hept-5-ene
• 英文别名: 2-hydroxy-2-methyl-1-[(1S,2R,3R,4R)-3-phenyl-2-bicyclo[2.2.1]hept-5-enyl]propan-1-one
• CAS: 637033-21-7
• 化学式: C₁₇H₂₀O₂
• 分子量: 256.345
• InChiKey: UVUCLNVCSNPFJZ-GBJTYRQASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,2R,3R,4R)-2-(2-hydroxy-2-methylpropanoyl)-3-phenylbicyclo[2.2.1]hept-5-ene 在 ammonium cerium(IV) nitrate 、 水 作用下， 以 乙腈 为溶剂， 反应 0.17h， 以85%的产率得到endo-5-carboxy-exo-6-phenylbicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  α‘-Hydroxy Enones as Achiral Templates for Lewis Acid-Catalyzed Enantioselective Diels−Alder Reactions

  摘要：

  alpha'-Hydroxy enones react with dienes in the presence of (S,S)-[Cu(tBu-box)](OTf)2 or (S,S)-[Cu(tBu-box)](SbF6)2 (2 to 10 mol %) to afford the corresponding Diels-Alder adducts in high yield and selectivity. Isomeric ratios (regioselectivity, endo/exo or cis/trans) of up to >99:1 and ee values of up to >99% are obtained. Significantly, difficult dienes such as isoprene, 2,3-dimethyl butadiene and piperylene behave satisfactorily. Subsequent oxidative cleavage of the ketol in the resulting cycloadducts by treatment with cerium ammonium nitrate (CAN) yields the corresponding enantiopure carboxylic acids. Alternatively, carbonyl addition and subsequent diol cleavage with CAN produces the corresponding ketone adducts.

  DOI：

  10.1021/ja0368002
• 作为产物：
  描述：

  3-羟基-3-甲基-2-丁酮 在 lithium hydroxide 、 [Cu((S,S)-tert-butyl-bis-(oxazoline))](SbF₆)2 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 14.0h， 生成 (1S,2R,3R,4R)-2-(2-hydroxy-2-methylpropanoyl)-3-phenylbicyclo[2.2.1]hept-5-ene
  参考文献：
  名称：

  α‘-Hydroxy Enones as Achiral Templates for Lewis Acid-Catalyzed Enantioselective Diels−Alder Reactions

  摘要：

  alpha'-Hydroxy enones react with dienes in the presence of (S,S)-[Cu(tBu-box)](OTf)2 or (S,S)-[Cu(tBu-box)](SbF6)2 (2 to 10 mol %) to afford the corresponding Diels-Alder adducts in high yield and selectivity. Isomeric ratios (regioselectivity, endo/exo or cis/trans) of up to >99:1 and ee values of up to >99% are obtained. Significantly, difficult dienes such as isoprene, 2,3-dimethyl butadiene and piperylene behave satisfactorily. Subsequent oxidative cleavage of the ketol in the resulting cycloadducts by treatment with cerium ammonium nitrate (CAN) yields the corresponding enantiopure carboxylic acids. Alternatively, carbonyl addition and subsequent diol cleavage with CAN produces the corresponding ketone adducts.

  DOI：

  10.1021/ja0368002

文献信息

• (1<i>R</i>)-(+)-Camphor and Acetone Derived α′-Hydroxy Enones in Asymmetric Diels−Alder Reaction: Catalytic Activation by Lewis and Brønsted Acids, Substrate Scope, Applications in Syntheses, and Mechanistic Studies
  作者：Patricia Bañuelos、Jesús M. García、Enrique Gómez-Bengoa、Ada Herrero、José M. Odriozola、Mikel Oiarbide、Claudio Palomo、Jesús Razkin

  DOI：10.1021/jo9023039

  日期：2010.3.5

  enones as reaction partners of the Diels−Alder reaction are shown, with especial focus on their potentials and limitations in solving the above difficult cases. α′-Hydroxy enones are able to bind reversibly to both Lewis acids and Brønsted acids, forming 1,4-coordinated species that are shown to efficiently engage in these inherently difficult Diels−Alder reactions. On these bases, a convenient control

  Diels-Alder反应构成了最强大，最趋同的C-C键形成转化之一，并且仍然是获得环己烯亚结构的特权途径，该环己烯亚结构广泛存在于天然产物和生物活性成分中。近年来，不对称的Diels-Alder催化方法取得了巨大进展，但仍然普遍存在固有的困难二烯-二烯亲和性组合，例如那些与环戊二烯相比反应活性较低的二烯或类似β-取代的丙烯酸酯和类似物的二烯亲和性。此处显示了作为Diels-Alder反应的反应伙伴的α'-羟基烯酮的主要特征，特别关注了它们在解决上述困难情况中的潜力和局限性。α'-羟基烯酮能够与路易斯酸和布朗斯台德酸可逆结合，形成了1,4-配位的物种，这些物种被证明可以有效地参与这些固有的困难的Diels-Alder反应。在这些基础上，可以使用樟脑衍生的手性α'-羟基烯酮模型（底物控制的不对称诱导）和路易斯酸或布朗斯台德酸催化，方便地控制反应的立体控制。作为这种方法的补充，还可以通过将简单
• α‘-Hydroxy Enones as Achiral Templates for Lewis Acid-Catalyzed Enantioselective Diels−Alder Reactions
  作者：Claudio Palomo、Mikel Oiarbide、Jesús M. García、Alberto González、Elena Arceo

  DOI：10.1021/ja0368002

  日期：2003.11.1

  alpha'-Hydroxy enones react with dienes in the presence of (S,S)-[Cu(tBu-box)](OTf)2 or (S,S)-[Cu(tBu-box)](SbF6)2 (2 to 10 mol %) to afford the corresponding Diels-Alder adducts in high yield and selectivity. Isomeric ratios (regioselectivity, endo/exo or cis/trans) of up to >99:1 and ee values of up to >99% are obtained. Significantly, difficult dienes such as isoprene, 2,3-dimethyl butadiene and piperylene behave satisfactorily. Subsequent oxidative cleavage of the ketol in the resulting cycloadducts by treatment with cerium ammonium nitrate (CAN) yields the corresponding enantiopure carboxylic acids. Alternatively, carbonyl addition and subsequent diol cleavage with CAN produces the corresponding ketone adducts.