methyl [(diphenylmethyl)imino] acetate N-oxide | 160030-82-0

• 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: methyl [(diphenylmethyl)imino] acetate N-oxide
• 英文别名: N-benzhydryl-2-methoxy-2-oxoethanimine oxide
• CAS: 160030-82-0
• 化学式: C₁₆H₁₅NO₃
• 分子量: 269.3
• InChiKey: PFBYNTXIMFDJEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-环己烯醇 、 methyl [(diphenylmethyl)imino] acetate N-oxide 在 4 A molecular sieve 、 Eu(fod)3 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 10.0h， 以71%的产率得到(3RS,3aSR,4SR,6aRS)-tetrahydro-1-diphenylmethyl-3,4-propano-1H,6H-furo[3,4-c]isoxazol-6-one
  参考文献：
  名称：

  在Eu（fod）3存在下，α-烷氧基羰基硝酮与乙烯基醚和烯丙醇的1,3-偶极环加成反应：硝酮的（Z）异构体的选择性活化

  摘要：

  α-alkoxycarbonylnitrones的非催化环加成1与乙烯基醚7，得到的混合物的顺式-和反式-cycloadducts 8，而铕（FOD）3的催化的环加成1与7，得到反式-cycloadducts反式- 8在高度立体选择性的方式。NMR研究表明，铕（FOD）3选择性地激活（ż）-nitrones（Ž） - 1中ë，ž -equilibrium硝酮的混合物1。相反，在Eu（fod）3存在下1与烯丙醇12的反应导致顺序酯基转移和分子内环加成反应产生分子内环加合物13。

  DOI：

  10.1016/j.tet.2006.10.014
• 作为产物：
  描述：

  乙醛酸甲酯 、 benzophenone oxime 以 苯 为溶剂， 以78%的产率得到methyl [(diphenylmethyl)imino] acetate N-oxide
  参考文献：
  名称：

  Studies on tandem transesterification and intramolecular cycloaddition of nitrones. 1. Sequential bicyclization of α-methoxycarbonylnitrones with allyl alcohols

  摘要：

  Treatment of alpha-methoxycarbonylnitrones with 5 equiv. of allyl alcohols in the presence of 1 equiv. of titanium tetraisopropoxide causes tandem transesterification, E,Z-isomerization of the nitrone moieties, and intramolecular cycloaddition to afford bicyclized compounds in one step. To reduce amounts of allyl alcohol, combined use of a catalytic amount of titanium tetraisopropoxide and molecular sieves 4A was found to be a more improved catalytic system, It was also found that reactions of (Z)-allyl alcohols with alpha-methoxycarbonylnitrone ate more facile than those of (E)-allyl alcohols. This aspect was extended to geometry differentiated cycloaddition.

  DOI：

  10.1016/0040-4020(94)00874-t

文献信息

• Tandem Transesterification and Intramolecular Cycloaddition of α-Methoxycarbonylnitrones with Chiral Acyclic Allyl Alcohols:  Systematic Studies on the Factors Affecting Diastereofacial Selectivity of the Cycloaddition
  作者：Osamu Tamura、Naka Mita、Toshiyuki Okabe、Tatsuya Yamaguchi、Chieko Fukushima、Masayuki Yamashita、Yasuhiro Morita、Nobuyoshi Morita、Hiroyuki Ishibashi、Masanori Sakamoto

  DOI：10.1021/jo001015i

  日期：2001.4.1

  secondary chiral (Z)-allyl alcohols are used, A(1,3)-strain arising from the chiralities in the (Z)-nitrone transition states of the intramolecular cycloaddtion is the most important factor. In contrast, in the case of the reaction using chiral nitrones 1c,d and (E)-allyl alcohols, steric interaction between the chiral N-substituent and the trans substituent of the olefin moiety in the intermediate

  系统地研究了影响α-甲氧基羰基硝酮1a-d与手性烯丙醇5或6酯交换反应而产生的中间α-烯丙氧基羰基硝酮的分子内环加成的立体化学过程的因素。发现非对映体选择的因素高度依赖于烯丙醇的几何形状。在使用伯或仲手性（Z）-烯丙基醇的情况下，由分子内环加成的（Z）-硝酮过渡态的手性引起的A（1,3）-菌株是最重要的因素。相反，在使用手性硝酮1c，d和（E）-烯丙基醇的反应的情况下，中间体中手性N-取代基与烯烃部分的反式取代基之间的空间相互作用占主导。这些方面适用于使用（E）-5和（Z）-5的混合物进行几何区分的环加成反应。作为一个典型的例子，在催化量的TiCl（4）和MS 4A存在下，用（E）-5和（Z）-5的1：1混合物处理大体积的1b，得到了4种中的主要产物7b。可能的产品。
• A Short-step Synthesis of 4-Hydroxyproline
  作者：Junko Hara、Yoshinobu Inouye、Hiroshi Kakisawa

  DOI：10.1246/bcsj.54.3871

  日期：1981.12

  The reaction of N-benzyl-, N-diphenylmethyl-, or N-(1-phenylpropyl)-α-methoxycarbonylmethanimine N-oxide newly prepared with acrylaldehyde in benzene, followed by hydrogenolysis over palladium hydroxide and by acid hydrolysis, gave 4-hydroxyprolines.

  新制备的 N-苄基-、N-二苯基甲基-或 N-（1-苯基丙基）-α-甲氧羰基甲亚胺 N-氧化物与丙烯醛在苯中反应，然后在氢氧化钯上进行氢解和酸水解，得到 4-羟基脯氨酸。
• Tamura, Osamu; Mita, Naka; Gotanda, Kentoku, Heterocycles, 1997, vol. 46, # 1, p. 95 - 99
  作者：Tamura, Osamu、Mita, Naka、Gotanda, Kentoku、Yamada, Ken-Ichi、Nakano, Tsuyoshi、Katagiri, Ruriko、Sakamoto, Masanori

  DOI：——

  日期：——
• One step bicyclization by way of tandem transesterification, intramolecular 1,3-dipolar cycloaddition of α-methoxycarbonylnitrones with allyl alcohols in the presence of titanium isopropoxide
  作者：Osamu Tamura、Tatsuya Yamaguchi、Katsuhide Noe、Masanori Sakamoto

  DOI：10.1016/s0040-4039(00)60602-0

  日期：1993.6

  Treatment of alpha-methoxycarbonylnitrones with allyl alcohols in the presence of titanium isopropoxide caused tandem transesterification, E,Z-isomerization and intramolecular cycloaddition to provide stereocontrolled polycyclic compounds in one step.
• Studies on tandem transesterification and intramolecular cycloaddition of nitrones. 1. Sequential bicyclization of α-methoxycarbonylnitrones with allyl alcohols
  作者：Osamu Tamura、Toshiyuki Okabe、Tatsuya Yamaguchi、Kentoku Gotanda、Katsuhide Noe、Masanori Sakamoto

  DOI：10.1016/0040-4020(94)00874-t

  日期：1995.1

  Treatment of alpha-methoxycarbonylnitrones with 5 equiv. of allyl alcohols in the presence of 1 equiv. of titanium tetraisopropoxide causes tandem transesterification, E,Z-isomerization of the nitrone moieties, and intramolecular cycloaddition to afford bicyclized compounds in one step. To reduce amounts of allyl alcohol, combined use of a catalytic amount of titanium tetraisopropoxide and molecular sieves 4A was found to be a more improved catalytic system, It was also found that reactions of (Z)-allyl alcohols with alpha-methoxycarbonylnitrone ate more facile than those of (E)-allyl alcohols. This aspect was extended to geometry differentiated cycloaddition.