1,2-dimethylenecycloheptane | 58738-52-6

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,2-dimethylenecycloheptane
• 英文别名: 1,2-bis(methylene)cycloheptane；1,2-dimethylidenecycloheptane；1,2-Dimethylencycloheptan；Cycloheptane, 1,2-bis(methylene)-
• CAS: 58738-52-6
• 化学式: C₉H₁₄
• 分子量: 122.21
• InChiKey: YBHCZUZCUFQDEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,2-dimethylenecycloheptane 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 5-methylenespiro<3.6>decane
  参考文献：
  名称：

  One-step spiroannulation using 1,2-bis(methylene)cycloalkane-magnesium reagents

  摘要：

  A one-step method for the synthesis of a wide variety of spirocyclic systems has been developed based on the reactions of bis-electrophiles with a series of new 1,3-diene-magnesium reagents, the magnesium complexes of 1,2-bis(methylene)cycloalkanes. The direct metalation of 1,2-bis(methylene)cycloalkanes with highly reactive magnesium in THF at ambient temperature generates the corresponding diene-magnesium reagents in high yields. Reactions of the diene-magnesium reagents with 1,n-dibromoalkanes produce a large number of spirocarbocycles containing an exocyclic double bond. The ring sizes of the accessible spiro compounds can be any combinations of four- to seven-membered rings. In most cases, the initially alkylated intermediates can be trapped by protonation, giving the corresponding bromo olefins. Significantly, treatment of the diene-magnesium reagents with bromoalkyl nitriles leads to a one-step synthesis of keto-functionalized spirocycles. The initial adduct is believed to be a Grignard reagent containing a cyano group. When a bromo nitrile containing a cyclic moiety is used as the bis-electrophile, the approach provides a direct access to dispiroenones.

  DOI：

  10.1021/jo00050a036
• 作为产物：
  描述：

  2-[(二甲氨基)甲基]环庚烷-1-酮 在 18-冠醚-6 、 potassium tert-butylate 、 silver(l) oxide 作用下， 以 乙醚 为溶剂， 60.0~120.0 ℃ 、0.13 Pa 条件下， 反应 14.5h， 生成 1,2-dimethylenecycloheptane
  参考文献：
  名称：

  光化学生成的二溴卡宾与 1,2-二亚甲基环烷烃的反应。1,4-加法是真实的

  摘要：

  Les dibromocarbenes thermiquement ou photochimiquement s'additionnent a divers dimethyl-1,2 cyclanes pour donner des produits d'addition-1,2 et -1,4

  DOI：

  10.1021/ja00204a024

文献信息

• Ru-Catalyzed Asymmetric Hydrogenative/Transfer Hydrogenative Desymmetrization of Meso-Epoxy Diketones
  作者：Yuping Hong、Jianzhong Chen、Zhenfeng Zhang、Yangang Liu、Wanbin Zhang

  DOI：10.1021/acs.orglett.6b01073

  日期：2016.6.3

  Via a strategy of asymmetric reductive desymmetrization, chiral cis-epoxy naphthoquinols with multiple contiguous stereocenters and functional groups were synthesized with excellent enantioselectivities (96–99% ee) and diastereoselectivities (8/1–15/1). A combined asymmetric hydrogenation/transfer hydrogenation mechanism was proposed based on experimental results.

  通过不对称还原去对称化的策略，合成了具有多个连续立体中心和官能团的手性顺式-环氧萘醌，具有优异的对映选择性（96-99％ee）和非对映选择性（8 / 1-15 / 1）。根据实验结果，提出了一种不对称加氢/转移加氢的联合机理。
• Diphosphination of 1,3-Dienes with Diphosphines under Visible-Light-Promoted Photoredox Catalysis
  作者：Nobutaka Otomura、Koji Hirano、Masahiro Miura

  DOI：10.1021/acs.orglett.8b03534

  日期：2018.12.21

  A diphosphination of 1,3-dienes with tetraaryldiphosphines proceeds under Ir(ppy)3-promoted photoredox catalysis to form the corresponding 1,4-diphosphino-2-butenes in good yields with good regioselectivity. The key to success is the addition of a Br+ additive. Subsequent double bond hydrogenation successfully delivers the 1,4-bis(diphenylphosphino)butane (DPPB) derivatives with uniquely large bite

  在Ir（ppy）3促进的光氧化还原催化下，用四芳基二膦进行1,3-二烯的二磷酸化反应，以良好的产率和良好的区域选择性形成相应的1,4-二膦基-2-丁烯。成功的关键是添加Br +添加剂。随后的双键氢化成功地提供了具有独特大咬合角的1,4-双（二苯基膦基）丁烷（DPPB）衍生物。因此，本方法可以容易地从容易获得的二烯底物接近DPPB型配体，该配体在过渡金属催化中非常重要。
• Pd(<scp>ii</scp>)-Catalyzed aerobic 1,2-difunctionalization of conjugated dienes: efficient synthesis of morpholines and 2-morpholones
  作者：Ke Wen、Zhengxing Wu、Buyun Chen、Jianzhong Chen、Wanbin Zhang

  DOI：10.1039/c8ob01291a

  日期：——

  methodology concerning the Pd(II)-catalyzed intermolecular difunctionalization of conjugated dienes is reported to synthesize a series of functionalized morpholines and 2-morpholones. Widely distributed and easily obtained β-amino alcohols and α-amino acids, as starting nitrogen and oxygen sources, are successfully applied in the difunctionalization of conjugated dienes respectively. The majority of the desired

  据报道，有关Pd（II）催化的共轭二烯分子间双官能化的一种新颖而有效的方法可合成一系列功能化的吗啉和2-吗啉酮。广泛分布且易于获得的β-氨基醇和α-氨基酸作为起始氮和氧源已分别成功地用于共轭二烯的双官能化。以中等至优异的产率获得了大多数所需产物。氧气已成功地用作末端氧化剂。产生的产物的进一步转化允许结构多样性的扩展。
• Studies on the formation of [5]metacyclophane
  作者：L.A.M. Turkenburg、P.M.L. Blok、W.H. de Wolf、F. Bickelhaupt

  DOI：10.1016/s0040-4039(01)81894-3

  日期：1981.1

  Base induced elimination of HCl from the dichloro[5.3.1]propellane gives a mixture of [5]metacyclophane () and tetrahydrocyclopentacyclooctenes (), while the stereoisomeric affords quantitatively.

  碱诱导的从二氯[5.3.1]丙炔中去除HCl时，形成[5]甲基环环烷（）和四氢环戊环辛烯（）的混合物，而立体异构体则定量提供。
• 3‐(Methoxycarbonyl)Cyclobutenone as a Reactive Dienophile in Enantioselective Diels–Alder Reactions Catalyzed by Chiral Oxazaborolidinium Ions
  作者：Peng Yan、Changxu Zhong、Jie Zhang、Yu Liu、Huayi Fang、Ping Lu

  DOI：10.1002/anie.202014308

  日期：2021.2.23

  Cyclobutenone has been used as a highly reactive dienophile in Diels–Alder reactions, however, no enantioselective example has been reported. We disclose herein a chiral oxazaborolidine‐aluminum bromide catalyzed enantioselective Diels–Alder reaction of 3‐alkoxycarbonyl cyclobutenone with a variety of dienes. Furthermore, a total synthesis of (−)‐kingianin F was completed for the first time via enantioenriched

  环丁烯酮已被用作Diels-Alder反应中的高反应性亲二烯体，但是，没有报道对映体选择性的例子。我们在此公开了3-烷氧基羰基环丁烯酮与各种二烯的手性恶唑硼烷-溴化铝催化的对映选择性Diels-Alder反应。此外，通过对映体富集的环加合物双环[4.2.0]辛烷衍生物首次完成了（-）-kingianin F的全合成。