(R)-(E)-(-)-4-Hydroxy-2-nonenenitrile | 134869-83-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-(E)-(-)-4-Hydroxy-2-nonenenitrile
• 英文别名: (2E,4R)-4-hydroxynon-2-enenitrile；(E,4R)-4-hydroxynon-2-enenitrile；(R)-4-hydroxy-nona-2-enonitrile；4(R)-hydroxynon-2(E)-enonitrile
• CAS: 134869-83-3
• 化学式: C₉H₁₅NO
• 分子量: 153.224
• InChiKey: FIVZAHDMDJAPCN-VPIOIWJLSA-N

物化性质

• 沸点：
  285.4±23.0 °C(Predicted)
• 密度：
  0.945±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  44
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(E)-(-)-4-Hydroxy-2-nonenenitrile 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 36.0h， 以97%的产率得到(R)-(-)-4-hydroxynonanenitrile
  参考文献：
  名称：

  Stereochemical Aspects of the Beckman Rearrangement of Oximes of Levoglucosenone and Its Dihydro Derivative. Enantioselective Synthesis of (+)- -Pelargonolactone

  摘要：

  Regiospecific C-5-halogenation with retention of configuration occurred upon Beckman fragmentation of levoglucosenone oxime using SOCl2 or PBr3. On the other hand, the oxime of its dihydro derivative gave under these conditions the C-6- substitution product. A stereoselective synthetic scheme for (+)-gamma-pelargonolactone, an attractant for the rice and corn weevils Sitophiltus zeamais, was developed from the fragmentation product of levoglucosenone oxime.

  DOI：

  10.1023/b:conc.0000018110.36123.f2
• 作为产物：
  描述：

  (R)-trans-2-octenal cyanohydrin acetate 在 双(乙腈)氯化钯(II) 作用下， 以 四氢呋喃 为溶剂， 生成 (R)-(E)-(-)-4-Hydroxy-2-nonenenitrile
  参考文献：
  名称：

  A Facile Synthesis of Optically Active γ-Cyanoallylic Alcohols Using Asymmetric Hydrocyanation of α,β-Alkenyl Aldehydes Followed by Stereospecific [3.3]Sigmatropic Chirality Transfer of the Cyanohydrin Acetates

  摘要：

  通过使用肽钛络合物催化α,β-烯基醛的不对称氰化反应，合成了光学活性的γ-氰基烯丙醇，得到高光学产率的α-氰基烯丙醇（氰基醇），随后通过钯络合物催化的相应乙酸酯的[3.3]σ迁移手性传递。

  DOI：

  10.1246/cl.1992.2443

文献信息

• Diastereoselective and Enantiospecific Synthesis of γ-Substituted α,β-Unsaturated Nitriles from O<i>-</i>Protected Allylic Cyanohydrins
  作者：Alejandro Baeza、Jesús Casas、Carmen Nájera、José M. Sansano

  DOI：10.1021/jo060239j

  日期：2006.5.1

  γ-Functionalized α,β-unsaturated nitriles are prepared diastereoselectively and enantiospecifically from enantioenriched cyanohydrin-O-phosphates and carbonates derived from α,β-unsaturated aldehydes, either by palladium or iridium-catalyzed nucleophilic allylic substitution reactions with different nucleophiles. Appropriate reaction conditions for dibenzylamine, benzylamine, sodium azide, NaOAc,

  γ-官能化的α，β-不饱和腈是通过钯或铱催化的亲核烯丙基烯丙基取代反应与不同的亲核试剂非对映地和对映体地由对映体富集的氰醇-O-磷酸酯和衍生自α，β-不饱和醛的碳酸盐制备的。描述了二苄基胺，苄基胺，叠氮化钠，NaOAc，乙酸四正丁铵（TBAA），苯酚和N-羟基琥珀酰亚胺的相应钠盐以及亲油性二甲基丙二酸酯钠的合适的反应条件。由巴豆醛衍生的不同取代的O保护的氰醇，例如碳酸盐和磷酸盐，（E）-己-2-烯，辛烯-2-烯，2-甲基丁-2-烯和肉桂醛用作烯丙基底物。取代发生时，（E）-γ-官能化腈的构型被完全保留，而Z-异构体的构型被反转。通常，氰醇-O-磷酸酯是获得最高E的首选材料。-非对映选择性。当使用脂肪族化合物和肉桂醛衍生物（高达98％dr）时，在钯或铱催化剂的存在下，二苄基胺是合成γ-氮化的α，β-不饱和腈的最佳亲核试剂。为了合成γ-氧化的α，β-不饱和腈钠或TBAA，选择试剂时避免在76％
• Binolam-AlCl: A Two-Centre Catalyst for the Synthesis of Enantioenriched CyanohydrinO-Phosphates
  作者：Alejandro Baeza、Carmen Nájera、José M. Sansano、José M. Saá

  DOI：10.1002/chem.200401290

  日期：2005.6.20

  The enantioselective synthesis of cyanohydrin O-phosphates by using in situ generated bifunctional catalysts (R)- or (S)-3,3'-bis(diethylaminomethyl)-1,1'-binaphthol-aluminium chloride (binolam-AlCl) is reported. The reaction, which can be described as an overall cyano-O-phosphorylation of aldehydes, has a wide scope and applicability. Evidence is also provided, including ab initio and DFT calculations

  报道了通过使用原位生成的双官能催化剂（R）-或（S）-3,3'-双（二乙基氨基甲基）-1,1'-联萘酚-氯化铝（binolam-AlCl）进行氰醇O-磷酸盐的对映选择性合成。可以描述为醛的整体氰基-O-磷酸化的反应具有广泛的范围和适用性。还提供了证据，包括从头算和DFT计算，以支持由路易斯酸/布朗斯台德碱（LABB）担当催化剂在首先诱导关键对映选择性氢氰化中的双重作用的支持，然后再进行O-磷酸化。简要筛选所得氰醇O-磷酸盐的合成有用性揭示了一些有趣的应用。其中包括化学选择性水解，还原和钯催化的亲核烯丙基取代，从而分别导致对映体富集的α-O-磷酸化的α-羟基酯，β-氨基醇和γ-氰基烯丙基醇。相应地合成天然存在的（-）-氨甲酰胺和（-）-aegeline。
• Synthesis of optically active γ-cyano-β, γ-epoxy alcohols and secondary γ-cyano allylic alcohols
  作者：Isao Yamakawa、Hirokazu Urabe、Yuichi Kobayashi、Fumie Sato

  DOI：10.1016/s0040-4039(00)78904-0

  日期：1991.4

  asymmetric epoxidation of 3-cyanoallyl alcohol (4-hydroxy-2-butenecarbonitrile, 6) afforded a potentially useful chiral building block, 3-cyano-2,3-epoxypropan-1-ol (7). Kinetic resolution of the secondary γ-cyano allylic alcohol (rac-3) provided an efficient method for synthesis of optically active 3. The Epoxidation of optically active 3 to γ-cyano-α,β-epoxy alcohol 5 was also reported.

  3-氰基烯丙基醇（4-羟基-2-丁烯腈，6）的Sharpless不对称环氧化提供了一种潜在有用的手性结构单元，3-cyano-2,3-epoxypropan-1-ol（7）。仲γ-氰基烯丙基醇（rac-3）的动力学拆分为合成旋光活性3提供了一种有效的方法。还报道了旋光性化合物3被环氧化为γ-氰基-α，β-环氧醇5。
• Catalytic Asymmetric Addition of Polyfunctional Dialkylzincs to .beta.-Stannylated and .beta.-Silylated Unsaturated Aldehydes
  作者：Roswitha Ostwald、Pierre-Yves Chavant、Heinz Stadtmueller、Paul Knochel

  DOI：10.1021/jo00094a027

  日期：1994.7

  The addition of functionalized dialkylzincs to readily available beta-stannylated or beta-silylated unsaturated aldehydes in the presence of a catalytic amount of (1R,2R)-1,2-bis(trifluorosulfonamido)cyclohexane (8 mol%) provides chiral allylic alcohols in good yields (60-90%) and excellent enantioselectivity (usually in the range of 85-95% ee). The synthetic utility of these allylic alcohols as chiral building blacks is demonstrated. The gamma-stannylated allylic alcohols were submitted to a Stille coupling leading to polyfunctional allylic alcohols and gamma-alkoxy enones. A treatment with CuCN in N-methylpyrrolidone at 130 degrees C provided chiral unsaturated gamma-hydroxy nitriles. Finally, the desilylation of the gamma-silylated alcohols gave chiral allylic alcohols having a terminal double bond. The catalytic asymmetric addition was found to show an important inverse temperature dependance. A mechanism for this addition is proposed.
• A Facile Synthesis of Optically Active γ-Cyanoallylic Alcohols Using Asymmetric Hydrocyanation of α,β-Alkenyl Aldehydes Followed by Stereospecific [3.3]Sigmatropic Chirality Transfer of the Cyanohydrin Acetates
  作者：Hiroshi Abe、Hideaki Nitta、Atsunori Mori、Shohei Inoue

  DOI：10.1246/cl.1992.2443

  日期：1992.12

  Optically active γ-cyanoallylic alcohols were synthesized by using asymmetric hydrocyanation of α,β-alkenyl aldehydes catalyzed by peptide-titanium complex to give α-cyanoallylic alcohols (cyanohydrins) with high optical yields followed by palladium complex catalyzed [3.3]sigmatropic chirality transfer of the corresponding acetates.

  通过使用肽钛络合物催化α,β-烯基醛的不对称氰化反应，合成了光学活性的γ-氰基烯丙醇，得到高光学产率的α-氰基烯丙醇（氰基醇），随后通过钯络合物催化的相应乙酸酯的[3.3]σ迁移手性传递。