3-boronoacrolein pinacolate | 535967-10-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 英文名称: 3-boronoacrolein pinacolate
• 英文别名: 3-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enal；3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)prop-2-enal
• CAS: 535967-10-3
• 化学式: C₉H₁₅BO₃
• 分子量: 182.027
• InChiKey: YVBIZZFCPNAJIA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.37
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  烯丙基硼酸频哪醇酯 、 3-boronoacrolein pinacolate 在 水 、 氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 49.0h， 以69%的产率得到(1E)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexa-1,5-dien-3-ol
  参考文献：
  名称：

  SN2' 硼介导的光信反应 - 取代烯酰胺和烯醇苯甲酸酯的新型一锅三组分合成

  摘要：

  (3-羟基-1-丙烯-1-基)硼酸酯转化为取代的烯酰胺和烯醇苯甲酸酯可以在一锅法中轻松实现，该程序由区域控制的Mitsunobu反应与方便的亲核试剂组成，然后是醛的烯丙基硼化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  DOI：

  10.1002/ejoc.200800965
• 作为产物：
  描述：

  3,3-diethoxy-1-propenylboronic acid pinacol ester 在 盐酸 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 以61%的产率得到3-boronoacrolein pinacolate
  参考文献：
  名称：

  Synthesis of Functionalized 1-Alkenylboronates via Hydroboration-Dealkylation of Alkynes with Diisopinocampheylborane

  摘要：

  Hydroborations of propargyl chloride, ethyl propiolate, 3-trimethyl-silyloxy-1-butyne, 1,1-diethoxy-2-propyne, 1-iodo- and 1-bromo-1-hexyne, and 1-bromo-3-chloro-1-propyne with diisopinocampheylborane 1, followed by dealkylation of the isopinocampheyl groups with acetaldehyde provide the corresponding 1-alkenylboronates in high yields with high regioselectivity.

  DOI：

  10.1080/00397919308012607

文献信息

• Stereoselective Synthesis of (+)-Goniodiol, (+)-Goniotriol, (-)-Goniofupyrone, and (+)-Altholactone Using a Catalytic Asymmetric Hetero-Diels-Alder/Allylboration Approach
  作者：Annaïck Favre、François Carreaux、Michael Deligny、Bertrand Carboni

  DOI：10.1002/ejoc.200800535

  日期：2008.10

  The stereoselective total synthesis of several members of the styryllactone family was achieved efficiently from common intermediate 8, prepared by a catalytic asymmetric inverse-electron-demand hetero-Diels–Alder/allylboration sequence. The transformation of 8 into α,β-unsaturated lactone led to the preparation of (+)-goniodiol (1) in a reduced number of steps. The epoxidation reaction was used to

  苯乙烯内酯家族的几个成员的立体选择性全合成是从普通中间体 8 有效地实现的，中间体 8 通过催化不对称逆电子需求异质狄尔斯-阿尔德/烯丙基硼化序列制备。将 8 转化为 α,β-不饱和内酯导致以减少的步骤数制备 (+)-goniodiol (1)。环氧化反应用于在 8 的内酯部分产生剩余的立体中心，然后将这些中间体加工成 (+)-goniotriol (2)、(-)-goniofupyrone (3) 和 (+)-altholactone ( 4) 通过异构化或环化步骤。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Catalytic Asymmetric Synthesis of a Potent Thiomarinol Antibiotic
  作者：Xuri Gao、Dennis G. Hall

  DOI：10.1021/ja042827p

  日期：2005.2.1

  and Gram-negative activity. The first total synthesis of a member of the thiomarinol class of marine antibiotics was achieved in a remarkable global yield of 22% (from 3-boronoacrolein pinacolate). The highlight of this synthesis is the efficient catalytic enantio-, regio-, E/Z-, and diastereoselective three-component inverse electron demand Diels-Alder/allylboration sequence. This key operation provides

  Thiomarinols，从细菌交替单胞菌 rava sp. 中分离出来。十一月 SANK 73390 是具有革兰氏阳性和革兰氏阴性活性的强效海洋抗生素。海洋抗生素 thiomarinol 类成员的首次全合成以 22% 的显着全球收率（来自 3-硼丙烯醛频哪酸酯）实现。该合成的亮点是高效的催化对映-、区域-、E/Z-和非对映选择性三组分逆电子需求 Diels-Alder/烯丙基硼化序列。这一关键操作提供了一个罕见的涉及无环 2-取代烯醇醚的对映选择性 HDA 反应的例子，它具有不寻常但偶然的动力学选择，有利于必要的 Z-亲二烯体。
• Synthesis and preliminary antibacterial evaluation of simplified thiomarinol analogs
  作者：Olivier Marion、Xuri Gao、Sandra Marcus、Dennis G. Hall

  DOI：10.1016/j.bmc.2008.01.001

  日期：2009.2

  derivatives was prepared by way of catalytic enantioselective inverse electron demand hetero [4 + 2] cycloaddition/allylboration tandem reaction. As a preliminary evaluation, these analogs were tested for antimicrobial activity using a standard disk diffusion assay. Whereas amide analogs were less active, the simple ester analogs 3 and 4 were demonstrated to be more active than thiomarinol H.

  通过催化对映选择性逆电子需量异[4 + 2]环加成/烯丙基化串联反应，制备了一系列简化的硫代水杨醇衍生物。作为初步评估，使用标准的磁盘扩散测定法测试了这些类似物的抗菌活性。酰胺类似物的活性较低，而简单的酯类似物3和4被证明比硫代马来醇H具有更高的活性。
• α-Hydroxyalkyl Heterocycles via Chiral Allylic Boronates: Pd-Catalyzed Borylation Leading to a Formal Enantioselective Isomerization of Allylic Ether and Amine
  作者：Stéphanie Lessard、Feng Peng、Dennis G. Hall

  DOI：10.1021/ja903946f

  日期：2009.7.22

  piperidinyl allylic boronates was achieved via a palladium-catalyzed borylation/isomerization reaction on the corresponding alkenyl triflates. The influence of the base and solvent was found to be crucial on the regio- and enantioselectivity of this reaction. The overall borylation process constitutes a successful example of formal asymmetric isomerization of allylic ether/amine. The resulting allylic boronate

  通过钯催化的相应烯基三氟甲磺酸酯的硼酸化/异构化反应，实现了合成有用的吡喃基和哌啶基烯丙基硼酸酯的有效催化对映选择性制备。发现碱和溶剂的影响对该反应的区域选择性和对映选择性至关重要。整个硼酸化过程构成了烯丙基醚/胺形式不对称异构化的成功例子。所得烯丙基硼酸酯试剂在一锅法中添加到各种醛中，以高立体选择性提供合成有用的 α-羟烷基衍生物。
• S_N2′ Boron-Mediated Mitsunobu Reactions - A New One-Pot Three-Component Synthesis of Substituted Enamides and Enol Benzoates
  作者：Fabienne Berrée、Nicolas Gernigon、Alain Hercouet、Chia Hui Lin、Bertrand Carboni

  DOI：10.1002/ejoc.200800965

  日期：2009.1

  The conversion of (3-hydroxy-1-propen-1-yl)boronates to substituted enamides and enol benzoates is readily achieved in a one-pot procedure consisting of a regiocontrolled Mitsunobu reaction with convenient nucleophiles, followed by allylboration of aldehydes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  (3-羟基-1-丙烯-1-基)硼酸酯转化为取代的烯酰胺和烯醇苯甲酸酯可以在一锅法中轻松实现，该程序由区域控制的Mitsunobu反应与方便的亲核试剂组成，然后是醛的烯丙基硼化。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)