methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenehexanoate | 1453202-92-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenehexanoate
• CAS: 1453202-92-0
• 化学式: C₁₃H₂₂O₅
• 分子量: 258.315
• InChiKey: QURQRUVNPWSSFG-UHFFFAOYSA-N

物化性质

• 沸点：
  305.1±35.0 °C(predicted)
• 密度：
  1.025±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methyl 3-((tert-butoxycarbonyl)oxy)-2-methylenehexanoate 、 苯甲酰甲酸 在 dipotassium hydrogenphosphate 、 Ru(2,2''-bipyrazine)₃(BF₄)₂ 作用下， 以 二甲基亚砜 为溶剂， 反应 24.0h， 以31%的产率得到methyl (Z)-2-(2-oxo-2-phenylethyl)hex-2-enoate
  参考文献：
  名称：

  α-酮酸与 Baylis-Hillman 碳酸盐在可见光光氧化还原催化下的脱羧偶联反应

  摘要：

  已经报道了通过可见光催化对 Baylis-Hillman 碳酸盐进行酰化。酰基由α-酮酸脱羧产生。该方法条件温和，底物范围广，官能团耐受性好，收率适中，为Baylis-Hillman衍生物的酰化提供了一条新途径。

  DOI：

  10.1016/j.poly.2021.115337

文献信息

• A Facile and Mild Synthesis of Trisubstituted Allylic Sulfones from Morita-Baylis-Hillman Carbonates
  作者：Lin Jiang、Yong-Gen Li、Jiang-Feng Zhou、Yong-Ming Chuan、Hong-Li Li、Ming-Long Yuan

  DOI：10.3390/molecules20058213

  日期：——

  An efficient and catalyst-free synthesis of trisubstituted allylic sulfones through an allylic sulfonylation reaction of Morita-Baylis-Hillman (MBH) carbonates with sodium sulfinates has been developed. Under the optimized reaction conditions, a series of trisubstituted allylic sulfones were rapidly prepared in good to excellent yields (71%–99%) with good to high selectivity (Z/E from 79:21 to >99:1). Compared with known synthetic methods, the current protocol features mild reaction temperature, high efficiency and easily available reagents.

  一种高效且不需要催化剂的合成三取代烯丙基磺酮的方法已被开发，该方法通过莫里塔-贝利斯-希尔曼（MBH）碳酸酯与亚硫酸钠的烯丙基磺酰化反应进行。在优化的反应条件下，一系列三取代烯丙基磺酮以良好至优异的产率（71%–99%）和良好至高选择性（Z/E从79:21到>99:1）迅速制备而成。与已知的合成方法相比，目前的方案具有温和的反应温度、高效性和易于获得的试剂。
• Reactivity of Morita–Baylis–Hillman Adducts in C–H Functionalization of (Hetero)aryl Nitrones: Access to Bridged Cycles and Carbazoles
  作者：Ashok Kumar Pandey、Dahye Kang、Sang Hoon Han、Heeyoung Lee、Neeraj Kumar Mishra、Hyung Sik Kim、Young Hoon Jung、Sungwoo Hong、In Su Kim

  DOI：10.1021/acs.orglett.8b01910

  日期：2018.8.3

  nitrones with Morita–Baylis–Hillman (MBH) adducts is described. An allylated intermediate derived from aryl nitrones and MBH adducts allows the formation of bridged cyclic compounds via an exotype [3 + 2] cycloaddition. In sharp contrast, electron-rich indolinyl or aniline substrates were found to couple with MBH adducts to generate naphthalene or carbazole derivatives, respectively.

  描述了铑（III）催化（杂）芳基硝酮与森田-贝利斯-希尔曼（MBH）加合物的交叉偶联。衍生自芳基硝酮和MBH加合物的烯丙基化中间体可通过外型[3 + 2]环加成反应形成桥环化合物。与之形成鲜明对比的是，发现富含电子的吲哚基或苯胺底物与MBH加合物偶合，分别生成萘或咔唑衍生物。
• The coupling of potassium organotrifluoroborates with Baylis–Hillman derivatives via visible-light photoredox catalysis
  作者：Hongqiang Ye、Qianwen Ye、Dongping Cheng、Xiaonian Li、Xiaoliang Xu

  DOI：10.1016/j.tetlet.2018.04.035

  日期：2018.5

  Catalyzed by Ir[dF(CF3)ppy]2(dtbbpy)PF6, the coupling of potassium organotrifluoroborates with Baylis–Hillman derivatives under visible light irradiation has been developed. Based on the mechanism of reductive quenching cycle, it provides an easy, mild, efficient method for the synthesis of a variety of α,β-unsaturated carboxylic esters derivatives in a broad scope of the substrates.

  在Ir [dF（CF 3）ppy] 2（dtbbpy）PF 6的催化下，开发了有机三氟硼酸钾与Baylis-Hillman衍生物在可见光下的偶联。基于还原淬灭循环的机理，它提供了一种简便，温和，有效的方法，可在广泛的底物中合成多种α，β-不饱和羧酸酯衍生物。
• The coupling of alkylboronic acids and esters with Baylis–Hillman derivatives by Lewis base/photoredox dual catalysis
  作者：Hongqiang Ye、He Zhao、Shujian Ren、Hongfeng Ye、Dongping Cheng、Xiaonian Li、Xiaoliang Xu

  DOI：10.1016/j.tetlet.2019.04.015

  日期：2019.5

  Utilizing Lewis base/photoredox dual catalysis, carbon radicals generated from either alkylboronic acids or esters were coupled with Baylis–Hillman derivatives under visible light irradiation. This protocol provides a mild and operationally simple method for the synthesis of a variety of α,β-unsaturated carbonyl compounds in a broad scope of the substrates. The mechanism of Lewis base activation and

  利用路易斯碱/光氧化还原双重催化，烷基硼酸或酯产生的碳自由基在可见光照射下与Baylis-Hillman衍生物偶联。该方案提供了一种温和且操作简单的方法，可在广泛的底物中合成各种α，β-不饱和羰基化合物。可能涉及路易斯碱活化和还原淬灭循环的机理。
• An Asymmetric Allylic Alkylation–Smiles Rearrangement–Sulfinate Addition Sequence to Construct Chiral Cyclic Sulfones
  作者：Quan-Gang Wang、Qing-Qing Zhou、Jin-Gen Deng、Ying-Chun Chen

  DOI：10.1021/ol402158u

  日期：2013.9.20

  An asymmetric allylic alkylation of Morita–Baylis–Hillman carbonates and β-keto sulfones was investigated by the catalysis of modified cinchona alkaloids, whose products underwent a Smiles rearrangement–sulfinate addition cascade to furnish highly functionalized five-membered cyclic sulfones in moderate to excellent enantioselectivity and good diastereoselectivity after treatment with DBU.

  通过修饰的金鸡纳生物碱的催化作用，研究了森田-贝利斯-希尔曼碳酸盐和β-酮砜的不对称烯丙基烷基化反应，其产物经历了微笑重排-亚磺酸盐加成级联反应，以中等至优异的对映选择性提供高度官能化的五元环砜DBU处理后具有良好的非对映选择性。