Benzyl-vinyl-carbamic acid tert-butyl ester | 142977-32-0

• 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: Benzyl-vinyl-carbamic acid tert-butyl ester
• 英文别名: Carbamic acid, ethenyl(phenylmethyl)-, 1,1-dimethylethyl ester；tert-butyl N-benzyl-N-ethenylcarbamate
• CAS: 142977-32-0
• 化学式: C₁₄H₁₉NO₂
• 分子量: 233.31
• InChiKey: GIWHBJSOVUGNAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Benzyl-vinyl-carbamic acid tert-butyl ester 在 diethylzinc 、 三氟乙酸 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 N-benzyl-N-<(1R*,2S*)-2-fluorocyclopropyl>amine
  参考文献：
  名称：

  对新一代喹诺酮羧酸DU-6859关键成分的合成研究。1.通过光学拆分合成（1 R，2 S）-2-氟环丙胺

  摘要：

  通过使用N-苄基-N-乙烯基氨基甲酸酯与锌-单氟乙炔化合物进行高度顺式选择性环丙烷化，形成的N-苄基-N-（顺式-2-氟环丙基）氨基甲酸酯脱保护以及所得产物的光学拆分，可以实现标题合成。 dl-顺式-2-氟环丙胺通过使用氯甲酸l-薄荷基酯作为拆分剂。关键的环丙烷化反应观察到的顺式选择性可以通过弯曲的过渡态模型来解释。

  DOI：

  10.1016/s0040-4020(01)89665-4
• 作为产物：
  描述：

  N-benzyl-N-(1-chloroethyl)carbamoyl chloride 在 sodium hydride 作用下， 以 四氢呋喃 、 paraffin 为溶剂， 生成 Benzyl-vinyl-carbamic acid tert-butyl ester
  参考文献：
  名称：

  对新一代喹诺酮羧酸DU-6859关键成分的合成研究。1.通过光学拆分合成（1 R，2 S）-2-氟环丙胺

  摘要：

  通过使用N-苄基-N-乙烯基氨基甲酸酯与锌-单氟乙炔化合物进行高度顺式选择性环丙烷化，形成的N-苄基-N-（顺式-2-氟环丙基）氨基甲酸酯脱保护以及所得产物的光学拆分，可以实现标题合成。 dl-顺式-2-氟环丙胺通过使用氯甲酸l-薄荷基酯作为拆分剂。关键的环丙烷化反应观察到的顺式选择性可以通过弯曲的过渡态模型来解释。

  DOI：

  10.1016/s0040-4020(01)89665-4

文献信息

• The Paternò-Büchi Reaction of α-Alkyl-Substituted Enecarbamates and Benzaldehyde
  作者：Thorsten Bach、Jürgen Schröder

  DOI：10.1055/s-2001-15075

  日期：——

  The α-substituted enecarbamates and enamides 5a-d, 5f and 6 were prepared in two steps from the corresponding ketone, N-benzylamine and an appropriate acylating agent (Boc2O, Ac2O). The [2+2] photocycloaddition reactions of benzaldehyde to the alkenes 5a-d which bear a primary or secondary alkyl substituent proceeded smoothly and gave the 3-aminooxetanes 8a-d in moderate to good yields (46-71 %). The α-phenyl-substituted enecarbamate 5f did not produce a photocycloaddition product presumably due to rapid energy transfer (triplet sensitization) from the photoexcited aldehyde. For less obvious reasons the tert-butyl-substituted enamide 6 did not react in the Paternò-Büchi reaction either. The 3-alkyl-3-aminooxetanes 8 were obtained as a mixture of cis- and trans-diastereoisomers. An increase in the steric bulk of the alkyl substituent R shifted the diastereomeric ratio (cis-8/trans-8) in the direction of the thermodynamically more stable cis-product (29:71 for R = CH3 up to 57:43 for R = cyclohexyl). The separated oxetane diastereoisomers cis-8a and trans-8a (R = CH3) underwent a smooth ring opening/cyclization reaction upon treatment with trifluoroacetic acid. Oxetane trans-8a yielded the oxazolidinones 9 and trans-10 (92 %), oxetane cis-8a gave exclusively the oxazolidinone cis-10 (54 %).

  α-取代的邻炔氨基甲酸酯和烯酰胺5a-d、5f和6是通过两步反应从相应的酮、N-苄胺和适当的酰化试剂（Boc2O、Ac2O）制备的。苯甲醛与具有一级或二级烷基取代基的烯烃5a-d的[2+2]光环加成反应顺利进行，得到3-氨基氟烯烃8a-d，产率中等到良好（46-71%）。α-苯基取代的邻炔氨基甲酸酯5f未能生成光环加成产物，这可能是由于光激发的醛迅速发生能量转移（三重态敏化）。由于不太明显的原因，叔丁基取代的烯酰胺6在Paternò-Büchi反应中也未发生反应。所得到的3-烷基-3-氨基氟烯烃8是顺式和反式二叠体异构体的混合物。烷基取代基R的立体阻碍增强使得二叠体比率（cis-8/trans-8）向热力学更稳定的顺式产物移动（R = CH3时为29:71，R = 环己基时为57:43）。分离得到的氟烯烃二叠体cis-8a和trans-8a（R = CH3）在三氟乙酸处理下顺利发生开环/环化反应。氟烯烃trans-8a产生了氧杂二氢吡啶酮9和trans-10（92%），而氟烯烃cis-8a则专一获得氧杂二氢吡啶酮cis-10（54%）。
• Photocatalytic Umpolung of <i>N</i>- and <i>O</i>-substituted alkenes for the synthesis of 1,2-amino alcohols and diols
  作者：Stephanie G. E. Amos、Stefano Nicolai、Jerome Waser

  DOI：10.1039/d0sc03655b

  日期：——

  organophotocatalytic 1,2-oxyalkynylation of ene-carbamates and enol ethers using Ethynyl BenziodoXolones (EBXs). 1-Alkynyl-1,2-amino alcohols and diols were obtained in up to 89% yield. Photocatalytic formation of radical cations led to Umpolung of the innate reactivity of the alkenes, enabling addition of a nucleophilic benzoate followed by radical alkynylation.

  我们报告使用乙炔基苯并基异戊二烯（EBXs）的烯氨基甲酸酯和烯醇醚的有机光催化1，2-氧炔基化。以高达89％的产率获得1-炔基-1,2-氨基醇和二醇。自由基阳离子的光催化形成导致烯烃固有反应性的发展，从而使得能够添加亲核苯甲酸酯，然后进行自由基炔基化。
• Paternò-Büchi Reactions of Silyl Enol Ethers and Enamides
  作者：Thorsten Bach、Florian Vogt、Kai Jödicke、Jürgen Schröder

  DOI：10.1055/s-0029-1217095

  日期：——

  aromatic aldehydes and silyl enol ethers in benzene as the solvent. The reactions occur with high simple diastereoselectivity and, when R¹ is chiral, with high facial diastereoselectivity. Under similar conditions, but in acetonitrile rather than benzene as the preferred solvent, the Paternò-Büchi reaction of N-acyl enamines (enamides) gives the corresponding protected 3-aminooxetanes. The cis-products

  3-（甲硅烷氧基）氧杂环丁烷是通过将芳族醛和甲硅烷基烯醇醚的混合物辐照在作为溶剂的苯中获得的。反应以高的简单非对映选择性发生，而当R 1为手性时，则以高的面部非对映选择性发生。在相似的条件下，但在乙腈而不是苯中作为优选溶剂，N-酰基烯胺（酰胺）的Paternò-Büchi反应得到相应的保护的3-氨基氧杂环丁烷。获得的顺式产物具有明显的简单非对映选择性。 环加成-杂环-氧杂环丁烷-帕特诺-布奇反应-光化学
• Synthesis and optical resolution of dl-cis-2-fluorocycloproplylamine, the key component of the new generation of quinolonecarboxylic acid, DU-6859
  作者：Osamu Tamura、Masaru Hashimoto、Yuko Kobayashi、Tadashi Katoh、Kazuhiko Nakatani、Masahiro Kamada、Isao Hayakawa、Toshifumi Akiba、Shiro Terashima

  DOI：10.1016/s0040-4039(00)92669-8

  日期：1992.6

  The title synthesis was accomplished by featuring highly cis-selective cyclpropanation of an N-vinylcarbamate with zinc-monofluorocarbenoid followed by deprotection of the formed N-(cis-2-fluorocyclopropyl)carbamate. Optical resolution of dl-cis-2-fluorocyclopropylamine was also achieved by employing l-menthyl chloroformate as a resolving agent.

  通过特征在于N-乙烯基氨基甲酸酯与锌-单氟类胡萝卜素的高度顺式-选择性环丙烷化，然后脱保护所形成的N-（顺式-2-氟环丙基）氨基甲酸酯，来完成标题合成。dl-顺-2-氟环丙胺的光学拆分也通过使用氯甲酸1-薄荷基酯作为拆分剂来实现。
• Photocycloaddition of <i>N</i>-Acyl Enamines to Aldehydes and Its Application to the Synthesis of Diastereomerically Pure 1,2-Amino Alcohols
  作者：Thorsten Bach、Jürgen Schröder

  DOI：10.1021/jo9819988

  日期：1999.2.1

  The regio- and stereoselective synthesis of the protected cis-3-aminooxetanes cis-5 and cis-7 is reported. The oxetanes were obtained by the photocycloaddition of aliphatic (6c-e) and aromatic (4, 6a) aldehydes to the corresponding enamides (1a-d,h) or enecarbamates (le-g). The enamine derivatives used in the Paterno-Buchi reaction were either commercially available or prepared from the corresponding acetaldehyde imines 2 by acylation. The oxetane formation proceeded with good-to-excellent simple diastereoselectivity for aromatic aldehydes (56-82% yield) and moderate selectivity for aliphatic aldehydes (46-55% yield). The cis-3-aminooxetanes are precursors for syn- and anti-1,2-amino alcohols. The relative configuration established in the photochemical step was retained upon nucleophilic ring opening between the oxygen atom and carbon atom C-4. By this means, syn-1,2-amino alcohols such as 8 and 10 were available in good yields. In contrast, the N-Boc-protected cis-3-aminooxetanes cis-5e and cis-5f were transformed into anti-1,2-amino alcohols. Upon treatment with trifluoroacetic acid, they underwent an intramolecular nucleophilic substitution at the carbon atom C-2 of the oxetane and the oxazolidinones II and 12 were formed. Because the substitution occurs with inversion of configuration, anti-1,2-amino alcohols, e.g., ephedrine (15), are accessible.