2-(Benzyloxy)-3-methylbutanal | 96925-01-8

• 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: 2-(Benzyloxy)-3-methylbutanal
• 英文别名: 2-benzoylisovaleraldehyde；3-methyl-2-phenylmethoxybutanal
• CAS: 96925-01-8
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: VUURQDUGKXVUFO-UHFFFAOYSA-N

物化性质

• 沸点：
  256.9±15.0 °C(Predicted)
• 密度：
  0.997±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(Benzyloxy)-3-methylbutanal 在 N-溴代丁二酰亚胺(NBS) 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 氘代氯仿 为溶剂， 反应 2.0h， 生成 (3S*,4R*)-Methyl 4-(benzyloxy)-3-bromo-2--5-methylhexanoate
  参考文献：
  名称：

  Stereoselective bromination of dehydroamino acids with controllable retention or inversion of olefin configuration

  摘要：

  Dehydroamino acid esters react with brominating reagents to produce syn-a-bromo imines as the major products, which undergo tautomerization to mixtures of the diastereomeric (E)- and (Z)-beta-bromo-alpha,beta-dehydroamino acids upon treatment with base. Herein, we examine the characteristics of dehydroamino acid substrates 1 that affect both the diastereofacial selectivity of the bromination and the configuration of the resulting olefin product(s) 3. In these studies, we demonstrate E- and Z-diastereoselectivity for this reaction using kinetic and thermodynamic reaction conditions. Z-Vinyl bromides were shown to be the thermodynamically more stable products and were formed from the kinetic E-isomers by DABCO-induced isomerization. High levels of kinetic E-selectivity were obtained by treatment of the intermediate alpha-bromo imines with hindered amine bases such as 2,2,6,6-tetramethylpiperidine or sodium hexamethyldisilazide. The reaction conditions detailed herein allow for the stereodivergent preparation of both E- and Z-vinyl bromide products from either diastereomeric E- or Z-olefin starting material with useful levels of diastereoselectivity.

  DOI：

  10.1021/jo00068a047
• 作为产物：
  描述：

  2-羟基-3-甲基丁酸 在 lithium aluminium tetrahydride 、 草酰氯 、 四丁基碘化铵 、 sodium hydride 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.75h， 生成 2-(Benzyloxy)-3-methylbutanal
  参考文献：
  名称：

  Stereoselective bromination of dehydroamino acids with controllable retention or inversion of olefin configuration

  摘要：

  Dehydroamino acid esters react with brominating reagents to produce syn-a-bromo imines as the major products, which undergo tautomerization to mixtures of the diastereomeric (E)- and (Z)-beta-bromo-alpha,beta-dehydroamino acids upon treatment with base. Herein, we examine the characteristics of dehydroamino acid substrates 1 that affect both the diastereofacial selectivity of the bromination and the configuration of the resulting olefin product(s) 3. In these studies, we demonstrate E- and Z-diastereoselectivity for this reaction using kinetic and thermodynamic reaction conditions. Z-Vinyl bromides were shown to be the thermodynamically more stable products and were formed from the kinetic E-isomers by DABCO-induced isomerization. High levels of kinetic E-selectivity were obtained by treatment of the intermediate alpha-bromo imines with hindered amine bases such as 2,2,6,6-tetramethylpiperidine or sodium hexamethyldisilazide. The reaction conditions detailed herein allow for the stereodivergent preparation of both E- and Z-vinyl bromide products from either diastereomeric E- or Z-olefin starting material with useful levels of diastereoselectivity.

  DOI：

  10.1021/jo00068a047

文献信息

• Aniline mediated oxidative C–C bond cleavage of α-alkoxy aldehydes in air and a model reaction for the synthesis of α-(d)-amino acid derivatives
  作者：Bin Hu、Yunfeng Li、Zhongjun Li、Xiangbao Meng

  DOI：10.1039/c3ob40685g

  日期：——

  4-methyl aniline mediated method for the oxidative C–C bond cleavage has been developed. The reaction proceeds in air using molecular oxygen as the oxidant, affording one-carbon shortened esters in moderate to good yields within a short time. Moreover, it provides a model reaction for the highly enantioselective synthesis of (D)-serine esters by combining with a L-proline catalyzed Mannich reaction.

  无金属和 4-甲基苯胺已经开发了介导的氧化碳-碳键裂解的方法。该反应使用分子氧作为氧化剂在空气中进行，在短时间内以中等至良好的收率提供了一个碳短的酯。而且，它通过与L-脯氨酸催化的曼尼希反应结合，为（D）-丝氨酸酯的高度对映选择性合成提供了模型反应。
• Additions of Organomagnesium Halides to α-Alkoxy Ketones: Revision of the Chelation-Control Model
  作者：Jacquelyne A. Read、Yingying Yang、K. A. Woerpel

  DOI：10.1021/acs.orglett.7b01161

  日期：2017.7.7

  obtained in additions of organometallic nucleophiles to α-alkoxy ketones but fails for reactions of allylmagnesium halides. Low diastereoselectivity in ethereal solvents results from no chelation-induced rate acceleration. Additions of allylmagnesium bromide to carbonyl compounds are diastereoselective using CH2Cl2 as the solvent even though rate acceleration is still absent. Stereoselectivity likely arises

  螯合控制模型解释了在α-烷氧基酮中添加有机金属亲核试剂后获得的高非对映选择性，但对卤代烯丙基镁的反应却失败了。在醚溶剂中的非对映选择性低是由于没有螯合引起的速率加速。使用CH 2 Cl 2作为溶剂，将烯丙基溴化镁加到羰基化合物上是非对映选择性的，尽管仍不存在速率加速作用。立体选择性可能源自溶液中螯合形式的优势。因此，提出了一种修正的螯合控制模型。
• Novel synthetic compounds, processes of manufacture and uses in the treatment of integrin-mediated disorders
  申请人：Cossio Pedro Fernando

  公开号：US20060211630A1

  公开（公告）日：2006-09-21

  This invention relates to nitroproline derivative compounds and procedures for their preparation and the preparation of pharmaceutical compositions containing the compounds. The invention also relates to the administration of compounds of the invention as agents for the treatment of mammalian diseases whose pathogenic and pathophysiological mechanisms depend on or are significantly contributed by undesirable cellular and molecular activities or responses induced by integrin-dependent molecular interactions.

  本发明涉及硝基脯氨酸衍生物化合物及其制备方法以及含有该化合物的药物组合物的制备。该发明还涉及将本发明的化合物作为治疗哺乳动物疾病的药剂的用途，该疾病的病原学和病理生理学机制取决于或主要受到不良细胞和分子活动或由整合素依赖的分子相互作用引起的不良反应的贡献。
• Kinetic Resolution of 1,1′-Biaryl-2,2′-Diols and Amino Alcohols through NHC-Catalyzed Atroposelective Acylation
  作者：Shenci Lu、Si Bei Poh、Yu Zhao

  DOI：10.1002/anie.201406192

  日期：2014.10.6

  We present here a highly efficient NHC‐catalyzed kinetic resolution of a wide range of 1,1′‐biaryl‐2,2′‐diols and amino alcohols to provide them in uniformly ≥99 % ee. This represents the first highly enantioselective catalytic acylation of axially chiral alcohols. The aldehyde backbone that is incorporated into the chiral acyl azolium intermediate was found to have a significant effect on the enantioselectivity

  我们在此展示了一种高效的NHC催化的动力学解析，适用于各种1,1'-联芳基-2,2'-二醇和氨基醇，可提供≥99％ee的均一性。这代表了轴向手性醇的首次高度对映选择性催化酰化。发现掺入手性酰基偶氮中间体中的醛主链对该方法的对映选择性具有显着影响。
• AN ASYMMETRIC SYNTHESIS OF α-BENZYLOXY ALDEHYDES HAVING A CHIRAL TERTIARY CENTER—AN APPLICATION TO THE ASYMMETRIC SYNTHESIS OF<i>exo</i>-(+)-BREVICOMIN—
  作者：Masatoshi Asami、Teruaki Mukaiyama

  DOI：10.1246/cl.1983.93

  日期：1983.1.5

  α-Benzyloxy aldehydes having a chiral tertiary center at α-carbon atom are synthesized in high enantiomeric excess by successive treatment of 2-methoxycarbonyl-3-phenyl-1,3-diazabicyclo[3.3.0]octane with diisobutylaluminum hydride (DIBAL-H) and Grignard reagents. The asymmetric reaction is applied to the total synthesis of exo-(+)-brevicomin.

  通过用氢化二异丁基铝（DIBAL-H）和格氏试剂连续处理 2-甲氧基羰基-3-苯基-1,3-二氮杂双环[3.3.0]辛烷，合成出对映体过量的、在 α 碳原子上具有手性叔中心的 α-苄氧基醛。该不对称反应被用于外-(+)-brevicomin 的全合成。