N-(2-chlorobenzylidene)-N-(1,1,1-trimethylsilyl)amine | 199604-10-9

• 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: N-(2-chlorobenzylidene)-N-(1,1,1-trimethylsilyl)amine
• 英文别名: N-trimethylsilyl-2-chlorobenzaldimine；1-(2-chlorophenyl)-N-trimethylsilylmethanimine
• CAS: 199604-10-9
• 化学式: C₁₀H₁₄ClNSi
• 分子量: 211.766
• InChiKey: NNRZMSWZOVUJIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(2-chlorobenzylidene)-N-(1,1,1-trimethylsilyl)amine 在 盐酸 、 silver hexafluoroantimonate 、 氯(三乙基膦)金(I) 、 水 作用下， 以 四氢呋喃 、 1,2-二氯乙烷 为溶剂， 反应 2.0h， 生成 (Z)-methyl 3-[(2SR,3SR)-2-(2-chlorophenyl)-2,3-dihydro-6-oxo-4-phenylpyrid-3-yl]propenoate
  参考文献：
  名称：

  Catalytic Intermolecular Hetero-Dehydro-Diels–Alder Cycloadditions: Regio- and Diasteroselective Synthesis of 5,6-Dihydropyridin-2-ones

  摘要：

  A novel catalyzed intermolecular heterodehydro-Diels-Alder reaction between push pull 1,3-dien-5-ynes and aldimines or silylaldimines is reported. The sequence is promoted both by gold(I) or silver(I) catalysts and leads to the diastereo- and regioselective formation of 5,6-dihydropyridin-2-ones.

  DOI：

  10.1021/ol202046y
• 作为产物：
  描述：

  2-氯苯甲醛 、 六甲基二硅氮烷 在 正丁基锂 作用下， 以 正己烷 为溶剂， 以69%的产率得到N-(2-chlorobenzylidene)-N-(1,1,1-trimethylsilyl)amine
  参考文献：
  名称：

  钯催化的多米诺直接芳基化/ N-芳基化：方便地合成菲啶

  摘要：

  多米诺反应具有从简单的起始原料产生复杂性的能力。公开了一种用于简便地构建各种菲啶衍生物的多米诺骨牌直接芳基化/ N芳基化的策略（参见方案； TMS =三甲基甲硅烷基，TBDMS =叔丁基二甲基甲硅烷基）。

  DOI：

  10.1002/anie.200902400

文献信息

• Formal Synthesis of Nitidine and NK109 via Palladium-Catalyzed Domino Direct Arylation/<i>N</i>-Arylation of Aryl Triflates
  作者：Mathieu Blanchot、David A. Candito、Florent Larnaud、Mark Lautens

  DOI：10.1021/ol200174g

  日期：2011.3.18

  The use of aryl triflates as reaction partners in a palladium-catalyzed domino direct arylation/N-arylation provides a great advantage due to the availability of starting materials. Furthermore, it allows expedient access to biologically interesting benzo[c]phenanthridine alkaloids.

  由于起始原料的可获得性，在钯催化的多米诺骨牌直接芳基化/ N-芳基化中使用芳基三氟甲磺酸酯作为反应伙伴具有很大的优势。此外，它允许方便地获得生物学上令人感兴趣的苯并[ c ]菲啶生物碱。
• N-Alkyloxycarbonyl-3-aryloxaziridines: Their Preparation, Structure, and Utilization As Electrophilic Amination Reagents
  作者：Joëlle Vidal、Stéphanie Damestoy、Laure Guy、Jean-Christophe Hannachi、André Aubry、Andreé Collet、André Aubry

  DOI：10.1002/chem.19970031019

  日期：1997.10

  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.
• The Critical Importance of Water in the Asymmetric Allylboration ofN-Trimethylsilylbenzaldimines withB-Allyldiisopinocampheylborane
  作者：Guang-Ming Chen、P. Veeraraghavan Ramachandran、Herbert C. Brown

  DOI：10.1002/(sici)1521-3773(19990315)38:6<825::aid-anie825>3.0.co;2-v

  日期：1999.3.15

  The free aldimine is probably the intermediate in the asymmetric allylboration of N-trimethylsilylaldimines in the presence of water (see scheme), which is critical for the reaction. The aldimine is rapidly captured by the allylborating agent. Ipc2 BAll=B-allyldiisopinocampheylborane.