methyl 2-((tert-butoxycarbonyloxy)(3-nitrophenyl)methyl)acrylate | 1312118-64-1

• 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: methyl 2-((tert-butoxycarbonyloxy)(3-nitrophenyl)methyl)acrylate
• 英文别名: Methyl 2-[(2-methylpropan-2-yl)oxycarbonyloxy-(3-nitrophenyl)methyl]prop-2-enoate
• CAS: 1312118-64-1
• 化学式: C₁₆H₁₉NO₇
• 分子量: 337.329
• InChiKey: INSPOYJQQALXDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  108
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2-((tert-butoxycarbonyloxy)(3-nitrophenyl)methyl)acrylate 在 三乙烯二胺 、 水 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以99%的产率得到3-羟基-2-亚甲基-3-(3-硝基苯基)丙酸甲酯
  参考文献：
  名称：

  Lewis Base Catalyzed Enantioselective Allylic Hydroxylation of Morita–Baylis–Hillman Carbonates with Water

  摘要：

  A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using O-18-labeling experiments.

  DOI：

  10.1021/jo201096e
• 作为产物：
  描述：

  3-羟基-2-亚甲基-3-(3-硝基苯基)丙酸甲酯 在 4-二甲氨基吡啶 、 二碳酸二叔丁酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 methyl 2-((tert-butoxycarbonyloxy)(3-nitrophenyl)methyl)acrylate
  参考文献：
  名称：

  通过新型[3 + 2]等靛蓝和MBH碳酸盐进行 有效和非对映选择性的双螺[cyclopent-3'-ene]双氧吲哚制备†

  摘要：

  已开发出一种新颖且非对映选择性的[3 + 2]等靛蓝和Morita–Baylis–Hillman碳酸盐，用于高效和一步制备带有两个全碳季铵盐的高空间二螺[cyclopent-3'-ene]双氧吲哚。在几分钟内，在温和条件下，螺中心和三个相邻的循环具有极好的收率（高达> 99％）和非对映选择性（高达> 20：1）。获得了一系列双螺[环戊-3'-烯]双恶吲哚，并进行了放大实验，结果极好，证明了该方案的潜在应用。

  DOI：

  10.1039/c7ob03009f

文献信息

• Highly Enantio- and Diastereoselective Synthesis of β-Methyl-γ-monofluoromethyl-Substituted Alcohols
  作者：Wenguo Yang、Xinle Wei、Yuanhang Pan、Richmond Lee、Bo Zhu、Hongjun Liu、Lin Yan、Kuo-Wei Huang、Zhiyong Jiang、Choon-Hong Tan

  DOI：10.1002/chem.201100929

  日期：2011.7.11

  Enanatiopure β‐methyl‐γ‐monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita–Baylis–Hillman carbonates. The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)2AQN. The origin of the stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly

  由氟双（苯磺酰基）甲烷与森田-贝利斯-希尔曼碳酸盐之间的烯丙基烷基化反应制备了纯的β-甲基-γ-一氟甲基醇。使用金鸡纳生物碱衍生物（DHQD）2 AQN催化反应。立体选择性的起源已通过DFT方法进行了验证。计算得出的各种过渡态的几何形状和相对能量强烈支持了所观察到的立体选择性。
• Phosphine-Catalyzed [3 + 2] Annulation of Morita–Baylis–Hillman Carbonates with Isoxazole-Based Alkenes
  作者：Jianning Liao、Jipan Dong、Jiaqing Xu、Wei Wang、Yongjun Wu、Yuxia Hou、Hongchao Guo

  DOI：10.1021/acs.joc.0c01948

  日期：2021.2.5

  A phosphine-catalyzed [3 + 2] annulation of Morita–Baylis–Hillman (MBH) carbonates with 3-methyl-4-nitro-5-styrylisoxazoles has been developed to afford various multifunctional isoxazoles in moderate to good yields with moderate to excellent diastereoselectivities. With a spirocyclic chiral phosphine as the catalyst, up to 89% ee was obtained.

  已开发出一种膦催化的森田-贝利斯-希尔曼（MBH）碳酸酯与3-甲基-4-硝基-5-苯乙烯基恶唑的碳酸盐环化反应[3 + 2]，以中等至良好的产率提供各种多功能异恶唑，具有中等至优异的非对映选择性。用螺环手性膦作为催化剂，获得高达89％的ee。
• Chiral bifunctional ferrocenylphosphine catalyzed highly enantioselective [3 + 2] cycloaddition reaction
  作者：Haiwen Hu、Shuxian Yu、Linglong Zhu、Lingxiu Zhou、Weihui Zhong

  DOI：10.1039/c5ob01958c

  日期：——

  A series of air-stable ferrocenylphosphines LB1–LB8 were designed and prepared in high yields. (R,SFc)-ferrocenylphosphine LB5 was found to efficiently promote the asymmetric [3 + 2] cycloaddition of Morita–Baylis–Hillman carbonates with maleimides to afford the corresponding bicyclic imides with 84–99% ee and 67–99% yield. Interestingly, the configuration of these products was contrary to those reported

  以高收率设计和制备了一系列空气稳定的二茂铁基膦LB1-LB8。（R，S Fc）-二茂铁基膦LB5被发现可以有效地促进Morita-Baylis-Hillman碳酸盐与马来酰亚胺的不对称[3 + 2]环加成反应，从而提供相应的双环酰亚胺，其ee为84-99％，产率为67-99％。有趣的是，这些产品的配置与文献报道的相反。
• Asymmetric allylic alkylation of Morita–Baylis–Hillman carbonates with α-fluoro-β-keto esters
  作者：Lin Yan、Zhiqiang Han、Bo Zhu、Caiyun Yang、Choon-Hong Tan、Zhiyong Jiang

  DOI：10.3762/bjoc.9.216

  日期：——

  available Cinchona alkaloid as catalyst, the asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates, with alpha-fluoro-beta-keto esters as nucleophiles, have been successfully developed. A series of important fluorinated adducts, with chiral quaternary carbon centres containing a fluorine atom, was achieved in good yields (up to 93%), with good to excellent enantioselectivities (up to 96%

  在市售的金鸡纳生物碱作为催化剂存在下，以 α-氟-β-酮酯为亲核试剂的 Morita-Baylis-Hillman 碳酸酯的不对称烯丙基烷基化已被成功开发。一系列重要的氟化加合物，其手性季碳中心含有一个氟原子，以良好的产率（高达 93%）获得，具有良好至极好的对映选择性（高达 96% ee）和中等非对映选择性（高达 4:1）博士）。
• Phosphine-Catalyzed Highly Enantioselective [3 + 3] Cycloaddition of Morita–Baylis–Hillman Carbonates with C,N-Cyclic Azomethine Imines
  作者：Lei Zhang、Honglei Liu、Guanyu Qiao、Zhanfeng Hou、Yang Liu、Yumei Xiao、Hongchao Guo

  DOI：10.1021/jacs.5b01138

  日期：2015.4.8

  The first phosphine-catalyzed highly enantioselective [3 + 3] cycloaddition of Morita-Baylis-Hillman carbonates with C,N-cyclic azomethine imines is described. Using a spirocyclic chiral phosphine as the catalyst, a novel class of pharmaceutically interesting 4,6,7,11b-tetrahydro-1H-pyridazino[6,1-a]iso-quinoline derivatives were obtained in high yields with good to excellent diastereoselectivities

  描述了第一个膦催化的 Morita-Baylis-Hillman 碳酸酯与 C,N-环状偶氮甲亚胺的高度对映选择性 [3 + 3] 环加成反应。使用螺环手性膦作为催化剂，以高产率获得了一类新的具有药学意义的 4,6,7,11b-四氢-1H-哒嗪并[6,1-a]异喹啉衍生物，具有良好到优异的非对映选择性和极其出色的对映选择性 (98->99% ee)。