(S)-2-pyridyloxirane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (S)-2-pyridyloxirane
• 英文别名: 2-[(2S)-oxiran-2-yl]pyridine
• 化学式: C₇H₇NO
• 分子量: 121.139
• InChiKey: DVZRYTWXFWRYPT-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  25.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-2-pyridyloxirane 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 2.33h， 生成 (R)-diphenyl (1-(pyridin-2-yl)-3,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butyl) phosphate
  参考文献：
  名称：

  通过立体特异性脱硼环化轻松获得环丙基硼酸酯：离去基团辅助激活双硼

  摘要：

  无过渡金属的脱硼环化策略导致外消旋和对映体富集的环丙基硼酸酯的有效合成。带有离去基团的双（硼酸盐）环化具有高度的非对映选择性和立体特异性，可耐受各种官能团和杂环。机理研究表明， γ-位的离去基团显着促进了宝石-二硼部分的活化。

  DOI：

  10.1002/anie.202302638
• 作为产物：
  描述：

  2-乙烯基吡啶 在 1-苯甲基-1,4-二氢烟酰胺 、 styrene monooxygenase from Sphingopyxis fribergensis Kp_5.2 、 腺嘌呤黄素 、 catalase from bovine liver 作用下， 以 二甲基亚砜 为溶剂， 反应 1.0h， 以99%的产率得到
  参考文献：
  名称：

  仿生苯乙烯单加氧酶酶级联介导的苯乙烯衍生物的不对称叠氮羟基化

  摘要：

  对映体富集的叠氮醇是有价值的手性氮丙啶和 1,2-氨基醇的前体，但其手性取代的类似物很难获得。我们建立了苯乙烯衍生物的不对称叠氮羟基化级联，通过酶促不对​​称环氧化生成手性取代的1,2-叠氮醇，然后进行区域选择性叠氮解，提供具有最多两个连续立体中心的叠氮醇。新分离的双组分黄素蛋白苯乙烯单加氧酶 StyA 被证明对烟酰胺辅酶仿生作为实用还原剂的环氧化具有高度选择性。与作为区域选择性开环的亲核试剂的叠氮化物结合，这种化学酶级联产生了高度对映体富集的芳香族 α-叠氮醇，转化率高达 >99%。双酶对应物与卤代醇脱卤酶催化的叠氮基解提供了替代的 β-叠氮醇异构体，其非对映异构体过量高达 94%。我们预计我们的生物催化级联将成为用双组分黄素蛋白单加氧酶更实际生产这些手性化合物的起点。

  DOI：

  10.1039/d1cy00855b

文献信息

• Microbiological transformations. Part 48: Enantioselective biohydrolysis of 2-, 3- and 4-pyridyloxirane at high substrate concentration using the Agrobacterium radiobacter AD1 epoxide hydrolase and its Tyr215Phe mutant
  作者：Yvonne Genzel、Alain Archelas、Jeffrey H Lutje Spelberg、Dick B Janssen、Roland Furstoss

  DOI：10.1016/s0040-4020(01)00146-6

  日期：2001.4

  The epoxide hydrolase (EH) from Agrobacterium radiobacter AD1 wild type (ArWT) and its Tyr215Phe mutant were compared for the biocatalyzed hydrolytic kinetic resolution (BHKR) of 2-, 3- and 4-pyridyloxirane. The regioselectivity of the oxirane ring opening as well as the substrate concentration limit and the inhibitory effect of the diol were determined. A gram scale preparation of enantiopure 2-pyridyloxirane

  比较了来自土壤杆菌放射杆菌AD1野生型（ArWT）及其Tyr215Phe突变体的环氧水解酶（EH）的2-，3-和4-吡啶基环氧乙烷的生物催化水解动力学拆分（BHKR）。测定环氧乙烷开环的区域选择性以及底物浓度极限和二醇的抑制作用。用这两种酶中的每一种都可以达到克级的对映体纯的2-吡啶基环氧乙烷（ee> 98％）的浓度，浓度高达127 mM（15.5 g / L）。
• Azidolysis of epoxides catalysed by the halohydrin dehalogenase from Arthrobacter sp. AD2 and a mutant with enhanced enantioselectivity: an (S)-selective HHDH
  作者：Ana Mikleušević、Ines Primožič、Tomica Hrenar、Branka Salopek-Sondi、Lixia Tang、Maja Majerić Elenkov

  DOI：10.1016/j.tetasy.2016.08.003

  日期：2016.10

  Halohydrin dehalogenase from Arthrobacter sp. AD2 catalysed azidolysis of epoxides with high regioselectivity and low to moderate (S)-enantioselectivity (E = 1-16). Mutation of the asparagine 178 to alanine (N178A) showed increased enantioselectivity towards styrene oxide derivatives and glycidyl ethers. Conversion of aromatic epoxides was catalysed by HheA-N178A with complete enantioselectivity, however the regioselectivity was reduced. As a result of the enzyme-catalysed reaction, enantiomerically pure (S)-beta-azido alcohols and (R)-alpha-azido alcohols (ee >= 99%) were obtained. (C) 2016 Published by Elsevier Ltd.
• Efficient biocatalysis for the production of enantiopure (S)-epoxides using a styrene monooxygenase (SMO) and Leifsonia alcohol dehydrogenase (LSADH) system
  作者：Hiroshi Toda、Ryouta Imae、Nobuya Itoh

  DOI：10.1016/j.tetasy.2012.09.017

  日期：2012.12

  Herein we report the production of enantiopure epoxides through biocatalysis using recombinant Escherichia coli cells expressing Rhodococcus sp. ST-10 styrene monooxygenase (SMO) and Leifsonia sp. S749 alcohol dehydrogenase (LSADH) genes are described. Rhodococcus sp. ST-10 SMO catalyzed the epoxidation of various alkenes, including styrene derivatives, vinyl pyridines, and linear alkenes, to give (S)-epoxides. NADH was regenerated by the reduction of NAD(+) by LSADH with 2-propanol. The E. coli biocatalyst was used in an aqueous/organic biphasic reaction system and the reaction conditions were optimized. Under the optimized conditions, 170 mM of (S)-styrene oxide was obtained from styrene in the organic phase with excellent enantiomeric excess (99.8%). This biocatalytic process was used to synthesize various (S)-epoxides. (C) 2012 Elsevier Ltd. All rights reserved.
• Styrene monooxygenase from Pseudomonas sp. LQ26 catalyzes the asymmetric epoxidation of both conjugated and unconjugated alkenes
  作者：Hui Lin、Jing Qiao、Yan Liu、Zhong-Liu Wu

  DOI：10.1016/j.molcatb.2010.08.012

  日期：2010.12

  A novel styrene monooxygenase (SMO) was isolated from Pseudomonas sp. LQ26, a styrene degrader from activated sludge. Sequence alignment demonstrated that it was the most distant member of all SMOs originating from the genus of Pseudomonas. The substrate spectrum of this enzyme extended beyond typical SMO substrates to 1-allylbenzene analogues, previously reported as non-substrates for the SMO from Pseudomonas fluorescens ST. The results demonstrate for the first time the asymmetric epoxidation of both conjugated and unconjugated alkenes catalyzed by SMO and suggest that a much broader substrate spectrum is expected for SMOs. (C) 2010 Elsevier B.V. All rights reserved.
• DNA-based hydrolytic kinetic resolution of epoxides
  作者：Ewold W. Dijk、Ben L. Feringa、Gerard Roelfes

  DOI：10.1016/j.tetasy.2008.10.004

  日期：2008.10

  DNA-bound copper(H) complexes serve as catalysts for the hydrolytic kinetic resolution of 2-pyridyloxiranes in water. Selectivity factors of up to 2.7 were achieved, indicating a chirality transfer of DNA to epoxides via a coordinated metal ion. (C) 2008 Elsevier Ltd. All rights reserved.