(R)-1-trimethylsilyloxy-1,2,3,4-tetrahydronaphthalene-1-carbonitrile

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (R)-1-trimethylsilyloxy-1,2,3,4-tetrahydronaphthalene-1-carbonitrile
• 英文别名: 1-(trimethylsilyloxy)-1,2,3,4-tetrahydronaphthalene-1-carbonitrile；1-trimethylsilyloxy-1,2,3,4-tetrahydronaphthalene-1-carbonitrile；(1R)-1-trimethylsilyloxy-3,4-dihydro-2H-naphthalene-1-carbonitrile
• 化学式: C₁₄H₁₉NOSi
• 分子量: 245.396
• InChiKey: AMMBOYWMOPYMGK-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3,4-二氢-1(2H)-萘酮 在 吡啶 、 盐酸 、 immobilized Pseudomonas cepacia lipase 、 水 、 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 83.0h， 生成 (S)-1-cyano-1,2,3,4-tetrahydronaphthalen-1-yl methoxyacetate 、 (R)-1-trimethylsilyloxy-1,2,3,4-tetrahydronaphthalene-1-carbonitrile
  参考文献：
  名称：

  Lipase catalyzed resolution of the quaternary stereogenic center in ketone-derived benzo-fused cyclic cyanohydrins

  摘要：

  The enantioselective preparation of both enantiomers of the benzo-fused cyanohydrin derived from alpha-tetralone via lipase catalyzed processes is described. The (S)-enantiomer has been obtained as the remaining substrate in the CAL-A catalyzed aminolysis of the methoxyacetylated derivative, using a structurally related amine as the nucleophile. The (R)-enantiomer has been obtained as the product of CAL-A or PSL-C catalyzed hydrolysis of the methoxyacetylated derivative in organic solvents. The resolutions of several structural analogs of this cyanohydrin have been also tested under similar conditions. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.07.004

文献信息

• Effective Activation of the Chiral Salen/Ti(OiPr)4 Catalyst with Achiral PhenolicN-Oxides as Additives in the Enantioselective Cyanosilylation of Ketones
  作者：Bin He、Fu-Xue Chen、Yan Li、Xiaoming Feng、Guolin Zhang

  DOI：10.1002/ejoc.200400411

  日期：2004.11

  the asymmetric cyanosilylation of ketones. By using 10 mol % of chiral salen-titanium(IV) complex in combination with 1 mol% achiral phenolic N-oxide as an additive, aromatic, aliphatic and heterocyclic ketones have been converted into the corresponding cyanohydrin trimethylsilyl ethers in 58-96% yields with 56-82% ee. Several factors concerning the reactivity and enantioselectivity have been discussed

  已发现手性钛 (IV) 配合物与酚类 N 氧化物添加剂的活化为酮的不对称氰基硅烷化提供了一种替代策略。通过使用 10 mol% 的手性 salen-titanium (IV) 配合物与 1 mol% 的非手性酚 N-氧化物作为添加剂，芳香族、脂肪族和杂环酮以 58-96% 的产率转化为相应的氰醇三甲基甲硅烷基醚含 56-82% ee。已经讨论了有关反应性和对映选择性的几个因素。已经提出了基于实验现象和研究的催化循环来解释这种活化和不对称诱导的起源。
• Enantioselective Cyanosilylation of Ketones Catalyzed by a Nitrogen-Containing Bifunctional Catalyst
  作者：Yan Xiong、Xiao Huang、Shaohua Gou、Jinglun Huang、Yuehong Wen、Xiaoming Feng

  DOI：10.1002/adsc.200505418

  日期：2006.3

  An efficient and optically active, bifunctional tetraaza ligand (2S)-N-(1R,2R)-2-[(S)-pyrrolidine-2-carboxamido]-1,2-diphenylethyl}pyrrolidine-2-carboxamide has been developed for the addition of trimethylsilyl cyanide (TMSCN) to ketones. The bifunctional catalyst system based on a monometallic titanium complex was found to be a highly enantioselective catalyst to provide O-TMS cyanohydrins with up

  一种高效且旋光的双官能四氮杂配体（2 S）-N -（1 R，2 R）-2-[（S）-吡咯烷-2-甲酰胺基] -1,2-二苯乙基}吡咯烷-2-甲酰胺已经开发出将三甲基甲硅烷基氰化物（TMSCN）添加到酮中的方法。发现基于单金属钛配合物的双官能催化剂体系是高度对映选择性的催化剂，其提供高达94％ee的O -TMS氰醇。已经提出了一种可能的过渡态来解释激活和不对称电感的起源。
• Enantioselective Cyanosilylation of Ketones by a Catalytic Double-Activation Method Employing Chiral Lewis Acid and Achiral <i>N</i>-Oxide Catalysts
  作者：Fuxue Chen、Xiaoming Feng、Bo Qin、Guolin Zhang、Yaozhong Jiang

  DOI：10.1021/ol034158a

  日期：2003.3.1

  [reaction: see text] Enantioselective addition of TMSCN to ketones is achieved by a catalytic double-activation method using 1a-Ti(IV) complex as the Lewis acid and achiral N-oxide 2 as the Lewis base to activate ketones and TMSCN, respectively.

  [反应：见正文]通过使用1a-Ti（IV）络合物作为路易斯酸和非手性N-氧化物2作为路易斯碱分别激活酮和TMSCN的催化双活化方法，实现了TMSCN对酮的对映选择性加成。 。
• Asymmetric cyanosilylation of ketones catalyzed by recyclable polymer-supported copper(II) salen complexes
  作者：Gurusamy Rajagopal、Shanmugam Selvaraj、Karuthamohamed Dhahagani

  DOI：10.1016/j.tetasy.2010.07.029

  日期：2010.9

  Various ketones have undergone asymmetric trimethylsilylcyanation at room temperature with (CH3)(3)SiCN (TMSCN) in the presence of a chiral-supported Cu(salen) complex and Ph3PO as the catalyst. Aromatic, aliphatic, and heterocyclic ketones have been converted into the corresponding cyanohydrin trimethylsilyl ethers in 83-96% yields with 52-84% ee. Several factors concerning the reactivity and enantioselectivity have been discussed. A double activation where Cu(salen) plays the role of Lewis acid and Ph3PO acts as a Lewis base is reported. Poly(ethylene glycol) monomethyl ether (MeO-PEG) has been used as a soluble support while JandaJel (JJ) and Merrifield (MF) resins served as insoluble supports. Each polymer is linked to the salen catalyst through a glutarate spacer. The soluble catalysts were recovered by precipitation with a suitable solvent while the insoluble catalysts were simply filtered from the reaction mixture. The JandaJel-attached Cu(salen) catalyst could be used for five cycles with the retention of efficiency and the Merrifield-bound Cu(salen) catalyst was found to loose activity with each use. (C) 2010 Published by Elsevier Ltd.
• Achiral phenolic N-oxides as additives: an alternative strategy for asymmetric cyanosilylation of ketones
  作者：Bin He、Fu-Xue Chen、Yan Li、Xiaoming Feng、Guolin Zhang

  DOI：10.1016/j.tetlet.2004.05.069

  日期：2004.7

  The activation of chiral titanium(IV) complexes with additives, phenolic N-oxides, is found to provide an alternative strategy for asymmetric cyanosilylation of ketones in excellent yield With LIP to 82%, ee. (C) 2004 Elsevier Ltd. All rights reserved.