(2-hydroxymethylphenyl)carbamic acid allyl ester | 345201-68-5

• 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-hydroxymethylphenyl)carbamic acid allyl ester
• 英文别名: allyl (2-(hydroxymethyl)phenyl)carbamate；prop-2-en-1-yl N-[2-(hydroxymethyl)phenyl]carbamate；prop-2-enyl N-[2-(hydroxymethyl)phenyl]carbamate
• CAS: 345201-68-5
• 化学式: C₁₁H₁₃NO₃
• mdl: MFCD20278488
• 分子量: 207.229
• InChiKey: RKPYLUUVRZHWGN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.181
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2-hydroxymethylphenyl)carbamic acid allyl ester 在 氯化亚砜 、 caesium carbonate 、 甲基磺酰氯 、 三乙胺 、 lithium chloride 、 copper dichloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 88.0h， 生成 1,2-Dimethyl-1,2,3,4-tetrahydroquinoline
  参考文献：
  名称：

  氮杂亚二甲苯基Diels–Alder方法用于天然存在的2-烷基四氢喹啉的合成

  摘要：

  最近发现的基于1,4-脱氢卤代反应的分子内氮杂二甲苯Diels-Alder反应在底物方面得到扩展，并留下了允许在两个合成步骤中组装四氢喹啉的基团。首次提出了使用三苯基膦和四氯甲烷（阿佩尔条件）进行硫代氨基甲酸酯的分子内裂解，得到氯甲基苯基异氰酸酯。该方法的合成可行性在生物碱rac -Angustureine和1-甲基-2-丙基四氢喹啉的第一批总合成中得到了证明。

  DOI：

  10.1016/s0040-4020(03)00915-3
• 作为产物：
  描述：

  邻硝基苯甲醇 在 铁粉 、 potassium carbonate 、 氯化铵 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 6.0h， 生成 (2-hydroxymethylphenyl)carbamic acid allyl ester
  参考文献：
  名称：

  A Convenient Allenoate-Based Synthesis of 2-Quinolin-2-yl Malonates and β-Ketoesters

  摘要：

  N-protected o-aminobenzaldehydes smoothly react with alpha,gamma- dialkylallenoates under Bronsted basic conditions to yield 2,3-disubstituted quinolines. This three step reaction cascade of Michael addition, aldol condensation, adn 1,3 N -> C rearrangement uses the complete protecting group as a building block in a highly efficient C,C-bond formation of a new all carbon quaternary center. Carbamate protected substrates (N-Boc, N-Cbz, N-Alloc) thus give 2-quinolin-2-yl-malonates, while amide protected substres (NAc,NBz) afford 2 quinolin 2-yl-beta-ketoesters in high yields.

  DOI：

  10.1021/ol502554e

文献信息

• Rhodium-Catalyzed Cycloisomerization Involving Cyclopropenes: Efficient Stereoselective Synthesis of Medium-Sized Heterocyclic Scaffolds
  作者：Frédéric Miege、Christophe Meyer、Janine Cossy

  DOI：10.1002/anie.201101220

  日期：2011.6.20

  Alloc=allyloxycarbonyl, Boc=tert‐butyloxycarbonyl). These reactions are the first examples of the formation of medium‐sized rings by the intramolecular cyclopropanation of an alkene with a donor‐substituted rhodium carbenoid, which is not generated from a diazo compound.

  令人满意的介质：环丙烯基甲醇和羧甲基胺的标题反应可生成带有[6.1.0]双环稠合至芳环的碳环和杂环（参见方案，Alloc =烯丙氧基羰基，Boc =叔丁氧基羰基）。这些反应是烯烃与供体取代的铑类胡萝卜素（不是由重氮化合物生成）通过分子内环丙烷化形成中等尺寸环的第一个例子。
• Designing and Accurately Developing a [6 + 2] Dipolar Cycloaddition for the Synthesis of Benzodiazocines
  作者：Wei Cai、Yiming Zhou、Yanlin He、Kaihong Chen、Cui Yu、You Huang

  DOI：10.1021/acs.orglett.1c01770

  日期：2021.7.16

  1,6-Dipolar cycloadditions represent a valuable strategy for the rapid construction of medium-sized rings. Herein, we describe the concept for the design of 1,6-dipoles that bypasses the regioselectivity. Through the introduction of an amino group into Morita–Baylis–Hillman (MBH) carbonates, unprecedented [6 + 2] dipolar cycloadditions were accurately developed with Cs2CO3, efficiently delivering a

  1,6-偶极环加成是快速构建中等大小环的一种有价值的策略。在此，我们描述了绕过区域选择性的 1,6-偶极子的设计概念。通过在 Morita-Baylis-Hillman (MBH) 碳酸酯中引入氨基，使用 Cs 2 CO 3准确开发了前所未有的 [6 + 2] 偶极环加成，在温和条件下有效地提供了一系列苯二氮卓类化合物。计算研究使人们对这种反应有了更深入的了解。
• DABCO catalyzed [4+2] annulations of Morita–Baylis–Hillman carbonates with isocyanates
  作者：Wei Cai、Yiming Zhou、Yanlin He、You Huang

  DOI：10.1039/d1cc03502a

  日期：——

  A highly concise method for 1,4-diazabicyclo[2.2.2]octane (DABCO) catalyzed [4+2] annulations of o-amino-acylation of aryl MBH carbonates with isocyanates has been developed. For the first time, MBH carbonates served as 1,4-dipoles, providing functionalized 3,4-dihydroquinazolinones in mild conditions with good to excellent yields. The density functional theory calculations of the mechanism supports

  已经开发了一种高度简洁的方法，用于 1,4-二氮杂双环 [2.2.2] 辛烷 (DABCO) 催化 [4+2]芳基 MBH 碳酸酯与异氰酸酯的邻氨基酰化反应。MBH 碳酸酯首次用作 1,4-偶极子，在温和的条件下提供功能化的 3,4-二氢喹唑啉酮，产率从高到高。该机制的密度泛函理论计算支持我们的假设。
• Convenient synthesis of <i>N</i>-alkyl-3,1-benzoxazin-2-ones from carbamate protected anthranil aldehydes and ketones <i>via</i> one-step alkylation/alkoxy rearrangement
  作者：Guang Tian、Wei-Li Jin、Chuanguang Qin、Jie Wang

  DOI：10.1039/d3ob00812f

  日期：——

  A practical and step-economical protocol was developed to prepare N-alkyl-3,1-benzoxazin-2-one derivatives from anthranil aldehydes and ketones via one-step alkylation/alkoxy rearrangement, where three new chemical bonds and one ring were constructed in a single step. Control studies revealed a stepwise mechanism and that the alkoxy rearrangement was an intermolecular process.

  开发了一种实用且经济的方案，通过一步烷基化/烷氧基重排从邻氨基苯甲醛和酮制备N-烷基-3,1-苯并恶嗪-2-酮衍生物，其中构建了三个新的化学键和一个环一步。对照研究揭示了逐步机制，并且烷氧基重排是分子间过程。
• Backbone Modifications of Aromatic Peptide Nucleic Acid (APNA) Monomers and Their Hybridization Properties with DNA and RNA
  作者：Lee D. Fader、Michael Boyd、Youla S. Tsantrizos

  DOI：10.1021/jo001650o

  日期：2001.5.1

  Aromatic peptide nucleic acid (APNA) monomers containing N-(2-aminobenzyl)-glycine, N-(2-aminobenzyl)-(R)- or -(S)-alanine, and N-(2-aminobenzyl)-beta -alanine moieties as part of their backbone were synthesized. These novel analogues were incorporated as a single "point mutation" in PNA hexamers, and their physicochemical properties were investigated by UV thermal denaturation and CD experiments. Destabilization in tripler formation between the PNA-APNA chimeras and complementary DNA or RNA oligomers was observed, as compared to the PNA control. The APNA monomer composed of the N-(2-aminobenzyl)-glycine backbone led to the smallest decrease in the thermal stability of the triplexes formed with DNA and RNA, while maintaining selectivity for base-pairing recognition. Since the PNA-APNA chimeras are more lipophilic than the corresponding PNA homopolymers, these oligomers may also exhibit better cell membrane permeability properties.