N-(1-hydroxymethyl-2,2-dimethyl-propyl)-benzamide | 383150-19-4

• 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: N-(1-hydroxymethyl-2,2-dimethyl-propyl)-benzamide
• 英文别名: (S)-N-(1-hydroxy-3,3-dimethylbutan-2-yl)benzamide；N-[(2S)-1-hydroxy-3,3-dimethylbutan-2-yl]benzamide
• CAS: 383150-19-4
• 化学式: C₁₃H₁₉NO₂
• 分子量: 221.299
• InChiKey: YVLUUDSOTDOGFA-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  49.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(1-hydroxymethyl-2,2-dimethyl-propyl)-benzamide 在 氯化亚砜 、 TEA 作用下， 以 乙醚 为溶剂， 反应 4.0h， 生成 (S)-4-tert-butyl-1,2-diphenyl-4,5-dihydroimidazole
  参考文献：
  名称：

  手性膦基咪唑啉配体的合成和应用：Ir催化的对映选择性氢化。

  摘要：

  [反应：见正文]合成了一系列在立体异构中心，咪唑啉环的氮原子和磷原子上具有不同取代基的手性膦基咪唑啉（PHIM配体）1a-j。已经评估了衍生自这些配体的铱配合物作为未官能化烯烃的对映选择性氢化的催化剂。在一些情况下，观察到的对映体过量高于类似的膦基-恶唑啉配体。

  DOI：

  10.1021/ol027253c
• 作为产物：
  描述：

  L-叔亮氨醇 、 苯甲酸酐 在 molybdenium(VI) dioxodichloride 作用下， 以 二氯甲烷 为溶剂， 反应 12.5h， 以96%的产率得到N-(1-hydroxymethyl-2,2-dimethyl-propyl)-benzamide
  参考文献：
  名称：

  Nucleophilic Acyl Substitutions of Anhydrides with Protic Nucleophiles Catalyzed by Amphoteric, Oxomolybdenum Species

  摘要：

  [GRAPHICS]Among six different group VIb oxometallic species examined, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. In contrast to the well-recognized redox chemical behaviors associated with oxomolybdenum(VI) species, the catalytic NAS was unprecedented and tolerates virtually all kinds of functional groups. By using benzoic anhydride as a mediator for in situ generation of an incipient mixed anhydride -MoO2Cl2 adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-alpha-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide, and trityl methacrylate syntheses with appropriate protic nucleophiles. The amphoteric character of the Mo=O unit in oxomolybdenum chlorides was found to be responsible for the catalytic NAS profile as supported by a control NAS reaction of using an authentic adduct-MoOCl2(O-2-CBut)(2) between pivalic anhydride and MoO2Cl2 as the catalyst.

  DOI：

  10.1021/jo048363v

文献信息

• Phosphorus-Based Organocatalysis for the Dehydrative Cyclization of <i>N</i>-(2-Hydroxyethyl)amides into 2-Oxazolines
  作者：Farzaneh Soleymani Movahed、Siong Wan Foo、Shogo Mori、Saeko Ogawa、Susumu Saito

  DOI：10.1021/acs.joc.1c02318

  日期：2022.1.7

  substrate scope and higher functional-group tolerance, providing the functionalized 2-oxazolines with retention of the configuration at the C(4) stereogenic center of the 2-oxazolines. Widely accessible β-amino alcohols can be used in this approach, and the cyclization of N-(2-hydroxyethyl)amides provides the desired 2-oxazolines in up to 99% yield. The mechanism of the reaction was studied by monitoring the

  由 1,3,5,2,4,6-三氮杂三膦促进的N- (2-羟乙基)酰胺环化为相应的 2-恶唑啉 (4,5-二氢恶唑) 的无金属仿生催化方案（TAP）衍生的有机催化剂三（邻苯二氧基）环三磷腈（TAP- 1）已被开发出来。与报道的相关系统相比，这种方法需要较少的预催化剂，就磷原子而言（最大转换数（TON）~30），并且表现出更广泛的底物范围和更高的官能团耐受性，提供了功能化的 2-恶唑啉保留在 2-恶唑啉的 C(4) 立体中心的构型。在这种方法中可以使用广泛易得的 β-氨基醇，并且N的环化-(2-羟乙基)酰胺以高达 99% 的收率提供所需的 2-恶唑啉。通过使用光谱和分析方法监测反应来研究反应机理，其中18 O-标记实验提供了有价值的见解。初始步骤涉及底物和 TAP- 1之间的化学计量反应，这导致催化剂、邻苯二酚环磷酸盐以及邻苯二酚磷酸盐和两种可能的活性中间体的原位生成。脱水环化也成功地以克级进行。
• Diastereoselective Transformation of Arenes into Highly Enantiomerically Enriched Substituted Cyclohexadienes
  作者：Gérald Bernardinelli、Sandra Gillet、E. Peter Kündig、Ronggang Liu、Alberto Ripa、Lionel Saudan

  DOI：10.1055/s-2001-17704

  日期：——

  path-ways reflect migratory aptitude to carbonylation. An X-ray structure determination of the phenyl oxazoline complex 3a allowed a rationalization of observed diastereoselectivity. Asymmetric induction was very high with the oxazoline and the SAMP-hydrazone complexes (>90% de) whereas the chiral benzaldehyde imine complex 8b afforded the substituted diene aldehydes in moderate enantiomeric purity (34-58%

  将 C-亲核试剂和 C-亲电试剂依次添加到对映体纯的芳烃三羰基铬配合物 3a、b、6 和 8b 中，其中含有芳基结合的手性恶唑啉、SAMP-腙和手性亚胺助剂，可提供取代的环己二烯。C-亲核试剂包括烷基-、乙烯基-和苯基-锂试剂。C-亲电体包括甲基碘、烯丙基溴、苄基溴和炔丙基溴。以 1,5,6-取代模式获得 1,3-环己二烯。结果与在络合芳烃的邻位进行非对映选择性外亲核加成，然后将亲电试剂加到金属中心是一致的。使用烯丙基、苄基和炔丙基，直接还原消除产生反式-5,6-取代产物。与碘甲烷，还原消除之前是 CO 插入，并且仅形成乙酰环己二烯，其原位去质子化/烷基化产生其中三个 C-取代基跨芳烃双键添加的产物，具有完全的区域和立体控制。这两种途径反映了羰基化的迁移能力。苯基恶唑啉配合物 3a 的 X 射线结构测定使观察到的非对映选择性合理化。恶唑啉和 SAMP-腙配合物 (>90% de) 的不对称诱导非常高，而手性苯甲醛亚胺配合物
• A Facile Synthesis of 2-Oxazolines via Dehydrative Cyclization Promoted by Triflic Acid
  作者：Tao Yang、Chengjie Huang、Jingyang Jia、Fan Wu、Feng Ni

  DOI：10.3390/molecules27249042

  日期：——

  oxazoline production. Herein, we report a triflic acid (TfOH)-promoted dehydrative cyclization of N-(2-hydroxyethyl)amides for synthesizing 2-oxazolines. This reaction tolerates various functional groups and generates water as the only byproduct. This method affords oxazoline with inversion of α-hydroxyl stereochemistry, suggesting that alcohol is activated as a leaving group under these conditions

  2-恶唑啉是许多天然产物、药物和功能共聚物中的常见部分。目前合成2-恶唑啉的方法主要依靠化学计量脱水剂或特定催化剂促进的催化脱水。这些条件要么产生化学计量的废物，要么需要强制共沸回流条件。因此，促进脱水环化同时不产生副产物的实用且稳健的方法将对恶唑啉生产具有吸引力。在此，我们报告了三氟甲磺酸 (TfOH) 促进的 N-(2-羟乙基) 酰胺脱水环化合成 2-恶唑啉。该反应容忍各种官能团并产生水作为唯一的副产物。该方法提供了 α-羟基立体化学反转的恶唑啉，表明在这些条件下酒精作为离去基团被激活。此外，还提供了直接从羧酸和氨基醇合成 2-恶唑啉的一锅法合成方案。
• Remote C–H bond functionalization reveals the distance-dependent isotope effect
  作者：Jiao-Jie Li、Ramesh Giri、Jin-Quan Yu

  DOI：10.1016/j.tet.2008.03.026

  日期：2008.7

  Iodination of remote aryl C-H bonds has been achieved using palladium acetate as the catalyst and iodoacetate (IOAc) as the oxidant. Systematic kinetic isotope studies imply a mechanistic regime shift as the number of bonds separating the directing heteroatom and the target C-H bond increases. Both isotope and electronic effects observed in remote C-H bond activation are consistent with an electrophilic palladation pathway in which the initial palladation is slower than the C-H bond cleavage. (C) 2008 Elsevier Ltd. All rights reserved.
• AcOLeDMAP and BnOLeDMAP: Conformationally Restricted Nucleophilic Catalysts for Enantioselective Rearrangement of Indolyl Acetates and Carbonates
  作者：Trisha A. Duffey、Scott A. Shaw、Edwin Vedejs

  DOI：10.1021/ja805541u

  日期：2009.1.14

  The rate of indotyl O- to C-acetyl or carboxyl rearrangement is accelerated by the electron-withdrawing N-diphenylacetyl group (DPA) using the conformationally restricted chiral catalysts AcOLeDMAP (12b) and BnOLeDMAP (13b). Highly enantioselective conversion to quaternary C-acetylated and C-carboxylated oxindoles is observed, even for substrates containing branched substituents. The rearrangement of the carboxylate substrates 19 occurs with complementary enantiofacial selectivity using catalyst 13b compared to the acetyl migrations of 16 catalyzed by 12b. Access to N-unsubstituted oxindoles is demonstrated by DPA cleavage with Et2NH.