methyl N-phenylmethylenecarbamate | 27593-61-9

• 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: methyl N-phenylmethylenecarbamate
• 英文别名: methyl benzylidenecarbamate；methyl N-benzylidenecarbamate
• CAS: 27593-61-9
• 化学式: C₉H₉NO₂
• 分子量: 163.176
• InChiKey: FQGYIIAXHJMRLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl N-phenylmethylenecarbamate 在 水 作用下， 以 丙酮 为溶剂， 以88%的产率得到N-methyl 1-hydroxy-1-phenylmethylcarbamate
  参考文献：
  名称：

  N-Alkyloxycarbonyl-3-aryloxaziridines: Their Preparation, Structure, and Utilization As Electrophilic Amination Reagents

  摘要：

  AbstractThis paper reports the synthesis of a series of N‐protected oxaziridines (N‐Moc, Boc, Z or Fmoc) and discusses their ability to deliver their N‐alkoxycar‐bonyl fragment to amines, enolates, sulfur, and phosphorus nucleophiles (electrophilic amination). These oxaziridines are prepared by oxidation of the corresponding imines with oxone or anhydrous MCPBA lithium salt as the source of oxygen. They transfer their N‐protected fragment to primary and secondary amines to give protected hydrazines in fair to excellent yield. The nitrogen transfer to free amino acids (in form of their R4N+ salts) is particularly fast, even at low temperature, providing L (or D) N‐protected α‐hydrazino acids. Enolates are C‐aminated to give N‐protected α‐amino ketones, esters, or amides in modest yield, due to a side aldol reaction of the unreacted enolate with the released benzaldehyde. With tertiary amines (Et3N), sulfides (PhSMe), and phosphines (Ph3P), amination and oxidation proceed in a parallel way; the amount of amination product increases when the temperature is lowered (kinetic control). Some of the factors that can orient the oxaziridine reactivity towards amination or oxidation of nucleophiles are considered.

  DOI：

  10.1002/chem.19970031019
• 作为产物：
  描述：

  苯甲醛二乙缩醛 在 盐酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 methyl N-phenylmethylenecarbamate
  参考文献：
  名称：

  Stavrovskaya,A.V. et al., Journal of Organic Chemistry USSR (English Translation), 1970, vol. 6, p. 18 - 22

  摘要：

  DOI：

文献信息

• Direct Catalytic Asymmetric Mannich Reaction with Dithiomalonates as Excellent Mannich Donors: Organocatalytic Synthesis of (<i>R</i>)-Sitagliptin
  作者：Han Yong Bae、Mun Jong Kim、Jae Hun Sim、Choong Eui Song

  DOI：10.1002/anie.201605167

  日期：2016.8.26

  enantioselectivity (up to 99 % ee). Furthermore, by the use of a DTM, even some highly challenging primary alkyl α‐amidosulfones were smoothly converted into the desired adducts with excellent enantioselectivity (up to 97 % ee), whereas the use of a malonate or monothiomalonate resulted in no reaction under identical conditions. The synthetic utility of the chiral Mannich adducts obtained from primary alkyl substrates

  在这项研究中，二硫代丙二酸酯（DTMs）被证明是在金鸡纳酸-二甲基酰胺催化的各种亚胺或α-酰胺基砜作为亚胺替代物的对映选择性曼尼希反应中的反应活性和立体选择性方面，是曼尼希高效供体。由于与传统丙二酸酯相比，DTM具有更高的反应活性，催化剂负载量可以降低至0.1 mol％，而不会损害对映选择性（最高ee达99％  ）。此外，通过使用DTM，即使是一些极富挑战性的伯烷基α-酰胺基砜也能以出色的对映选择性（高达ee高达97％）平稳地转化为所需的加合物。 ），而丙二酸酯或一硫代丙二酸酯的使用在相同条件下不会导致反应。从一级烷基底物获得的手性曼尼希加合物的合成效用通过抗糖尿病药（-）-（R）-西他列汀的有机催化，无偶联剂-无合成得到了强调。
• Radical Addition of Ethers to Imines Initiated by Dimethylzinc
  作者：Ken-ichi Yamada、Hidetaka Fujihara、Yasutomo Yamamoto、Yoshihisa Miwa、Tooru Taga、Kiyoshi Tomioka

  DOI：10.1021/ol0266572

  日期：2002.10.1

  Ethers undergo addition to imines in the presence of dimethylzinc and air through a radical process. [reaction: see text]

  醚在二甲基锌和空气存在下通过自由基过程加成亚胺。[反应：看文字]
• High Performance of <i>N</i>-Alkoxycarbonyl-imines in Triethylborane-Mediated Tin-Free Radical Addition
  作者：Ken-ichi Yamada、Takehito Konishi、Mayu Nakano、Shintaro Fujii、Romain Cadou、Yasutomo Yamamoto、Kiyoshi Tomioka

  DOI：10.1021/jo2025042

  日期：2012.2.3

  Triethylborane-mediated tin-free radical alkylation of N-alkoxycarbonyl-imines, such as N-Boc-, N-Cbz-, and N-Teoc-imines, proceeded smoothly at a low temperature (−78 to −20 °C) to give the corresponding adducts in high yield. Although the formation of isocyanate was the major unfavorable reaction at room temperature, a one-pot conversion of N-Boc-imine to N-ethoxycarbonyl-adduct was possible through

  三乙基硼烷介导的N-烷氧基羰基-亚胺（例如N- Boc-，N- Cbz-和N- Teoc-亚胺）的锡自由基烷基化在低温（-78至-20°C）至以高收率得到相应的加合物。尽管异氰酸酯的形成在室温下是主要的不利反应的一锅转化N-将Boc-亚胺ñ -乙氧羰基的加合物通过在原位产生的相应的异氰酸酯是可能的。N-烷氧基羰基-亚胺比N- Ts-和N具有更高的性能-PMP-亚胺通过烷氧基羰基的适度吸电子特征而合理化，该特征使烷基的添加和由三乙基硼烷有效地捕获所形成的氨基自由基都快速地进行。
• Thermal Hetero [3 + 2] Cycloaddition of Dipolar Trimethylenemethane to<i>N</i>-Sulfonyl and<i>N</i>-Acyl Imines. Synthesis of<i>γ</i>-Amino Acid Derivatives
  作者：Shigeru Yamago、Masao Yanagawa、Eiichi Nakamura

  DOI：10.1246/cl.1999.879

  日期：1999.9

  Thermal hetero [3 + 2] cycloaddition reaction of a dipolar trimethylenemethane 2 with an N-acyl or N-tosyl imine gives an α-methylene-γ-pyrrolidone acetal 4 in high yield, which upon hydrolysis affords a γ-amino acid derivative.

  偶极三亚甲基甲烷 2 与 N-酰基或 N-甲苯磺酰亚胺的热杂 [3 + 2] 环加成反应以高产率得到 α-亚甲基-γ-吡咯烷酮缩醛 4，水解后得到 γ-氨基酸衍生物。
• N-amination using N-methoxycarbonyl-3-phenyloxaziridine. Direct access to chiral N_β-protected α-hydrazinoacids and carbazates
  作者：Joëlle Vidal、Jacques Drouin、André Collet

  DOI：10.1039/c39910000435

  日期：——

  Primary and secondary amines N–H, including α-aminoacids, can be converted under mild conditions to the corresponding carbazates N–NH–CO2Me, on reaction with N-methoxycarbonyl-3-phenyloxaziridine 1.

  初级和次级胺的 N–H，包括 α-氨基酸，可以在温和条件下与 N-甲氧基碳酰基-3-苯基呋喃啶 1 反应，转化为相应的脲体 N–NH–CO2Me。