(1R,2S)-trans-2-hydroxy-1-cyanocyclohexane trimethyl silyl ether | 182698-20-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (1R,2S)-trans-2-hydroxy-1-cyanocyclohexane trimethyl silyl ether
• 英文别名: (1R,2S)-2-trimethylsilyloxy-cyclohexane-1-carbonitrile；(1R,2S)-2-trimethylsilyloxycyclohehane-1-carbonitrile；2-((trimethylsilyl)oxy)cyclohexane-1-carbonitrile；(1S,2R)-(2-cyanocyclohexyloxy)trimethylsilane；(1R,2S)-2-trimethylsilyloxycyclohexane-1-carbonitrile
• CAS: 182698-20-0
• 化学式: C₁₀H₁₉NOSi
• 分子量: 197.352
• InChiKey: MOJPZIXGLYGBKZ-ZJUUUORDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,2S)-trans-2-hydroxy-1-cyanocyclohexane trimethyl silyl ether 以 甲醇 、 三氟乙酸 为溶剂， 反应 1.0h， 以66%的产率得到(1R,2S)-2-羟基环己烷-1-腈
  参考文献：
  名称：

  Asymmetric Ring Opening of Meso Epoxides with TMSCN Catalyzed by (pybox)lanthanide Complexes

  摘要：

  [GRAPHICS]The asymmetric ring opening of meso epoxides with TMSCN is catalyzed by (pybox)YbCl3 complexes, yielding the beta-trimethylsilyloxy nitrile ring-opened products with good enantioselectivities (83-92% ee). The reaction exhibits a second-order kinetic dependence on catalyst concentration and a first-order dependence on epoxide concentration, consistent with a bimetallic pathway involving simulataneous activation of epoxide and cyanide.

  DOI：

  10.1021/ol005721h
• 作为产物：
  描述：

  氧化环己烯 在 chiral yttrium BINAP(NH₂)2-derived catalyst 作用下， 以 正己烷 为溶剂， 生成 (1S,2R)-trans-2-hydroxy-1-cyanocyclohexane trimethylsilyl ether 、 (1R,2S)-trans-2-hydroxy-1-cyanocyclohexane trimethyl silyl ether
  参考文献：
  名称：

  Exceptionally Active Yttrium−Salen Complexes for the Catalyzed Ring Opening of Epoxides by TMSCN and TMSN₃

  摘要：

  Halide or alkoxide free yttrium-salen complexes are excellent catalysts for the ring opening of epoxides mediated by TMSCN and TMSN3. Substrate to catalyst ratios up to 10000 have been realized in these potentially useful reactions, which can be run under solvent-free conditions. Even though the enantioselectivities for the TMSCN-mediated reaction remains modest (best 77% ee), these studies with a highly tunable ligand system may provide further impetus for work in this important area of catalysis. Even though attempts to isolate a Y-cyanide complex, which was detected by in situ IR spectroscopy, failed, a related dimeric hydroxide complex was isolated. A kinetic study using in situ IR spectroscopy did not provide conclusive data to assign an order with respect to Y in this reaction.

  DOI：

  10.1021/jo071076h

文献信息

• Enantiotopic Discrimination by Coordination‐Desymmetrized <i>meso</i> ‐Ligands
  作者：Yutang Li、Anna Lidskog、Helena Armengol‐Relats、Thanh Huong Pham、Antoine Favraud、Maxime Nicolas、Sami Dawaigher、Zeyun Xiao、Dayou Ma、Emil Lindbäck、Daniel Strand、Kenneth Wärnmark

  DOI：10.1002/cctc.201902243

  日期：2020.3.19

  coordination of different metal ions at enantiotopic positions of an achiral meso‐ligand are reported. These catalysts exhibit a pseudo‐Cs symmetry and are able to catalyze reactions demanding simultaneous involvement of two catalytic sites. The latter was demonstrated by application in the asymmetric ring‐opening of meso‐epoxides.

  的是，由于在非手性对映的位置不同的金属离子的配位是手性的对映纯的仅仅催化剂的第一实施例的内消旋报告-配体。这些催化剂表现出伪C s对称性，并且能够催化需要同时参与两个催化位点的反应。后者是通过在非对称开环应用程序演示了内消旋环氧化物。
• Chiral Ti(IV) complexes of hexadentate Schiff bases as precatalysts for the asymmetric addition of TMSCN to aldehydes and the ring opening of cyclohexene oxide
  作者：Yuri N. Belokon、Denis Chusov、Dmitry A. Borkin、Lidia V. Yashkina、Andrey V. Dmitriev、Dmitry Katayev、Michael North

  DOI：10.1016/j.tetasy.2006.08.009

  日期：2006.9

  Chiral dinuclear titanium(IV) complexes (generated in situ from hexadentate Schiff bases and titanium tetra-isopropoxide) have been found to be more effective catalysts for the asymmetric addition of trimethylsilyl cyanide to aldehydes and the ring opening of cyclohexene oxide than their mononuclear analogues. The best results were obtained for benzaldehyde (86% enantiomeric excess) and cyclohexene

  已发现手性二核钛（IV）配合物（由六齿席夫碱和四异丙氧基钛原位生成）比单核类似物更有效地催化三甲基甲硅烷基氰化物不对称加成到醛和环己烯氧化物的开环。苯甲醛（对映体过量86％）和氧化环己烯（对映体过量89％）获得了最佳结果。
• Developing a Biocascade Process: Concurrent Ketone Reduction-Nitrile Hydrolysis of 2-Oxocycloalkanecarbonitriles
  作者：Elisa Liardo、Nicolás Ríos-Lombardía、Francisco Morís、Javier González-Sabín、Francisca Rebolledo

  DOI：10.1021/acs.orglett.6b01510

  日期：2016.7.15

  cell-catalyzed nitrile hydrolysis in one-pot. The first step, mediated by ketoreductases, involved a dynamic reductive kinetic resolution, which led to 2-hydroxycycloalkanenitriles in very high enantio- and diastereomeric ratios. Then, the simultaneous exposure to nitrile hydratase and amidase from whole cells of Rhodococcus rhodochrous provided the corresponding 2-hydroxycycloalkanecarboxylic acids with excellent

  将2-氧代环烷烃腈的立体选择性生物还原反应与一锅内全细胞催化的腈水解反应同时进行。由酮还原酶介导的第一步涉及动态还原动力学拆分，这导致2-羟基环烯基腈的对映体和非对映体比例很高。然后，同时暴露于杜鹃红球菌全细胞的腈水合酶和酰胺酶，为全酶级联反应提供了具有优异的总收率和光学纯度的相应的2-羟基环烷羧酸。
• Polymer-Bound Pyridine-Bis(oxazoline). Preparation through Click Chemistry and Evaluation in Asymmetric Catalysis
  作者：Mélanie Tilliet、Stina Lundgren、Christina Moberg、Vincent Levacher

  DOI：10.1002/adsc.200700112

  日期：2007.9.3

  A pyridine-bis(oxazoline) ligand was efficiently immobilized by copper(I)-catalyzed azide-alkyne cycloaddition onto a polystyrene resin. The so obtained click-pybox resin 1a was associated with various metal salts (YbCl3, LuCl3, CuOTf) and the resulting resin-bound catalysts were explored in ring-opening of cyclohexene oxide, silylcyanation of benzaldehyde and alkynylation of imines. These new polymer-supported

  通过铜（I）催化的叠氮化物-炔烃环加成反应将吡啶-双（恶唑啉）配体有效地固定在聚苯乙烯树脂上。如此获得的点击式box盒树脂1a与各种金属盐（YbCl 3，LuCl 3，CuOTf）缔合，并在环己烯氧化物的开环，苯甲醛的甲硅烷基氰化和亚胺的炔基化反应中探索了与树脂结合的催化剂。这些新型的聚合物负载型催化剂在催化活性，对映选择性和可回收性方面表现出良好至优异的性能。
• Asymmetric ring opening of epoxides with cyanides catalysed by chiral binuclear titanium complexes
  作者：Victor I. Maleev、Denis A. Chusov、Lidiya V. Yashkina、Nikolai S. Ikonnikov、Michail M. Il’in

  DOI：10.1016/j.tetasy.2014.04.012

  日期：2014.5

  A series of Schiff bases obtained from salicylaldehydes and 3,3′-diformyl-BINOL were synthesized. The complexes of these Schiff bases with Ti(IV) were active for the asymmetric ring opening of epoxides with TMSCN. A mixture of unpurified ligands was found to be as effective as the best one. The influence of temperature, solvent polarity and structural modification of the pre-catalysts on the enantioselectivity

  合成了一系列从水杨醛和3,3'-二甲酰基-BINOL获得的席夫碱。用的Ti（IV）这些席夫碱的复合物的活性与TMSCN环氧化物的不对称环开口。未纯化的配体的混合物被发现是作为最好的一个是有效的。还研究了温度，溶剂极性和预催化剂的结构改性对方法对映选择性的影响。