4-(4-chlorophenyl)-4-vinyl-1,3-dioxolan-2-one | 1459246-68-4

• 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: 4-(4-chlorophenyl)-4-vinyl-1,3-dioxolan-2-one
• CAS: 1459246-68-4
• 化学式: C₁₁H₉ClO₃
• 分子量: 224.644
• InChiKey: BKRSXVKQBXOWLD-UHFFFAOYSA-N

物化性质

• 沸点：
  374.7±42.0 °C(Predicted)
• 密度：
  1.380±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.89
• 重原子数：
  15.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-(4-chlorophenyl)-4-vinyl-1,3-dioxolan-2-one 在 sodium tetrahydroborate 、 [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate 、 双(2-二苯基磷苯基)醚 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成
  参考文献：
  名称：

  A Domino Process toward Functionally Dense Quaternary Carbons through Pd-Catalyzed Decarboxylative C(sp³)–C(sp³) Bond Formation

  摘要：

  An efficient protocol was developed to construct functionally dense quaternary carbons with concomitant formation of a new Csp(3)-Csp(3) bond via Pd-catalyzed decarboxylative transformation of vinyl cyclic carbonates. This redox-neutral catalytic system features stereocontrolled formation of multisubstituted allylic scaffolds with an aldehyde functionality generated in situ, and it typically can be performed at room temperature without any additives. DFT calculations provide a rationale toward the selective formation of these compounds and reveal a complex mechanism that with the help of microkinetic models is able to reproduce the nontrivial dependence of the identity of the product on the nature of the substituents in the substrate.

  DOI：

  10.1021/jacs.7b12608
• 作为产物：
  描述：

  在 吡啶 、 三光气 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 4-(4-chlorophenyl)-4-vinyl-1,3-dioxolan-2-one
  参考文献：
  名称：

  Palladium-Catalyzed [5 + 2] Annulation of Vinylethylene Carbonates with Barbiturate-Derived Alkenes

  摘要：

  A palladium/XantPhos-catalyzed [5 + 2] annulation of VECs with electron-deficient alkenes having an isolated carbon-carbon double bond has been developed to afford spirobarbiturate-tetrahydrooxepines. This study provides an expedient assembly of biologically interesting spirobarbiturate-tetrahydrooxepines. The easy scalability and versatile transformability of the reaction products were also exhibited.

  DOI：

  10.1021/acs.orglett.0c02508

文献信息

• Asymmetric Allylic Etherification of Vinylethylene Carbonates with Diols via Pd/B Cooperative Catalysis: A Route to Chiral Hemi-Crown Ethers
  作者：Sardaraz Khan、Hongfang Li、Can Zhao、Xue Wu、Yong Jian Zhang

  DOI：10.1021/acs.orglett.9b03663

  日期：2019.12.6

  carbonates (VECs) with diols has been developed. By using cooperative catalysts of the chiral palladium complex and triethylborane in mild conditions, the process gave monoetherified and bisetherified polyglycol derivatives with tetrasubstituted stereocenters in high yields with complete regioselectivities and high levels of enantio- and diastereoselectivities.

  已经开发了钯催化碳酸乙烯基亚乙酯（VEC）与二醇的区域和对映选择性烯丙基醚化反应。通过在温和条件下使用手性钯配合物和三乙基硼烷的协同催化剂，该方法可以高产率获得具有四取代立体中心的单醚化和双醚化的聚乙二醇衍生物，具有完全的区域选择性以及高水平的对映和非对映选择性。
• Palladium-Catalyzed Diastereoselective Formal [5 + 3] Cycloaddition for the Construction of Spirooxindoles Fused with an Eight-Membered Ring
  作者：Ben Niu、Xiao-Yun Wu、Yin Wei、Min Shi

  DOI：10.1021/acs.orglett.9b01748

  日期：2019.6.21

  A Pd-catalyzed formal [5 + 3] intermolecular cycloaddition reaction of isatin-derived α-(trifluoromethyl)imines with aryl substituted vinylethylene carbonates (VECs) has been reported, affording trifluoromethyl-group-containing spirooxindoles fused with an eight-membered ring as a single diastereoisomer in good yields in the presence of a Brønsted acid in a one-pot manner under mild conditions. The

  据报导，钯衍生的Isatin衍生的α-（三氟甲基）亚胺与芳基取代的乙烯基碳酸亚乙酯（VEC）的形式[5 + 3]的分子间环加成反应，提供了含三氟甲基的螺环新多烯与八元环稠合而成在温和的条件下，在布朗斯台德酸的存在下，以一锅法以高收率得到一个单一的非对映异构体。还使用手性膦配体实现了该反应的不对称形式，同时将得到的产物进一步转化以在氧化时得到螺氧基吲哚并吡咯烷衍生物。
• Expedient Dual Co/Organophotoredox Catalyzed Stereoselective Synthesis of All‐Carbon Quaternary Centers
  作者：Àlex Cristòfol、Bart Limburg、Arjan W. Kleij

  DOI：10.1002/anie.202103479

  日期：2021.7.5

  An efficient and attractive Co/organophotoredox dual catalysis protocol has been developed allowing the stereoselective access to a wide variety of syn-configured 1,3-diols featuring quaternary carbon centers. The synthesis of the target molecules is achieved under ambient reaction conditions using modular and accessible reagents, substituted vinyl cyclic carbonates and aldehydes, and in short reaction

  已经开发了一种高效且有吸引力的 Co/有机光氧化还原双催化方案，允许立体选择性地访问各种具有四元碳中心的同构 1,3-二醇。目标分子的合成是在环境反应条件下使用模块化和易接近的试剂、取代的乙烯基环状碳酸酯和醛，在很短的反应时间内完成的。机械控制实验表明，立体选择性可以通过优选的 Zimmerman-Traxler 过渡态合理化，该过渡态包含 Co（烯丙基）物质和活化的醛。因此，这种新开发的工艺扩展了贱金属催化在构建具有挑战性的季碳立体中心中的应用。
• Chiral Bidentate Phosphoramidite-Pd Catalyzed Asymmetric Decarboxylative Dipolar Cycloaddition for Multistereogenic Tetrahydrofurans with Cyclic <i>N</i>-Sulfonyl Ketimine Moieties
  作者：Hao-Peng Lv、Xiao-Peng Yang、Bai-Lin Wang、Hao-Di Yang、Xing-Wang Wang、Zheng Wang

  DOI：10.1021/acs.orglett.1c01411

  日期：2021.6.18

  An asymmetric [3 + 2] cycloaddition of vinyl ethylenecarbonates (VECs) and (E)-3-arylvinyl substituted benzo[d] isothiazole 1,1-dioxides has been developed using the Pd complex of a bidentate phosphoramidite (Me-BIPAM) as the catalyst, providing a wide variety of chiral multistereogenic vinyltetrahydrofurans in good yields with excellent diastereo- and enantioselectivities (up to >20:1 dr, 99% ee)

  使用二齿亚磷酰胺 (Me-BIPAM) 的 Pd 配合物开发了乙烯基碳酸亚乙酯 (VEC) 和 ( E )-3-芳基乙烯基取代的苯并[ d ] 异噻唑 1,1-二氧化物的不对称 [3 + 2] 环加成反应该催化剂以良好的收率提供多种手性多立体乙烯基四氢呋喃，并具有出色的非对映选择性和对映选择性（高达 >20:1 dr，99% ee）。
• Enantioselective Construction of Tertiary C–O Bond via Allylic Substitution of Vinylethylene Carbonates with Water and Alcohols
  作者：Ajmal Khan、Sardaraz Khan、Ijaz Khan、Can Zhao、Yuxue Mao、Yan Chen、Yong Jian Zhang

  DOI：10.1021/jacs.7b04759

  日期：2017.8.9

  tertiary C-O bond via asymmetric allylic substitution of racemic vinylethylene carbonates with water and alcohols has been developed. Under the cooperative catalysis system of an in situ generated chiral palladium complex and boron reagent in mild conditions, the process allowed rapid access to valuable tertiary alcohols and ethers in high yields with complete regioselectivities and high enantioselectivities

  已经开发了一种通过外消旋乙烯基碳酸亚乙酯与水和醇的不对称烯丙基取代对映选择性构建叔 CO 键的有效方法。在温和条件下原位生成的手性钯配合物和硼试剂的协同催化系统下，该过程允许以高产率快速获得有价值的叔醇和醚，具有完整的区域选择性和高对映选择性。该协议代表了与作为氧供体的水直接对映选择性形成三级 CO 键的第一个例子。该过程的合成效用已通过将产品加工成生物相关制剂的关键中间体来证明，