(R)-4-溴-1,2-环氧基丁烷 | 79413-93-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 中文名称: (R)-4-溴-1,2-环氧基丁烷
• 英文名称: (R)-4-Brom-1,2-epoxybutan
• 英文别名: (S)-(-)-4-Brom-1,2-epoxybutan；(R)-4-bromo-1,2-epoxybutane；(R)-4-bromo-1,2-butylene epoxide；2-bromoethyloxirane；2-(R)-(2-bromo-ethyl)-oxirane；(R)-(2-bromoethyl)oxirane；(2R)-2-(2-Bromoethyl)oxirane
• CAS: 79413-93-7
• 化学式: C₄H₇BrO
• 分子量: 151.003
• InChiKey: ZKODPGZNBMIZFX-SCSAIBSYSA-N

物化性质

• 沸点：
  110 °C(Press: 45 Torr)
• 密度：
  1.588±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  6
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-4-溴-1,2-环氧基丁烷 、 可可碱 在 sodium hydride 作用下， 以 二甲基亚砜 为溶剂， 反应 0.33h， 生成 (R)-3,7-dimethyl-1-(2-(oxiran-2-yl)ethyl)-1H-purine-2,6(2H,6H)-dione
  参考文献：
  名称：

  Predictable Stereoselective and Chemoselective Hydroxylations and Epoxidations with P450 3A4

  摘要：

  Enantioselective hydroxylation of one specific methylene in the presence of many similar groups is debatably the most challenging chemical transformation. Although chemists have recently made progress toward the hydroxylation of inactivated C-H bonds, enzymes such as P450s (CYPs) remain unsurpassed in specificity and scope. The substrate promiscuity of many P450s is desirable for synthetic applications; however, the inability to predict the products of these enzymatic reactions is impeding advancement. We demonstrate here the utility of a chemical auxiliary to control the selectivity of CYP3A4 reactions. When linked to substrates, inexpensive, achiral theobromine directs the reaction to produce hydroxylation or epoxidation at the fourth carbon from the auxiliary with pro-R facial selectivity. This strategy provides a versatile yet controllable system for regio-, chemo-, and stereoselective oxidations at inactivated C-H bonds and demonstrates the utility of chemical auxiliaries to mediate the activity of highly promiscuous enzymes.

  DOI：

  10.1021/ja200551y
• 作为产物：
  描述：

  4-溴-1,2-环氧丁烷 在 (acetao)(aqua)(S,S)-N,N′-bis(3,5-di-tert-butylsalicylidene-1,2-cyclohexanediamino)-cobalt(III) 、 水 作用下， 以 四氢呋喃 为溶剂， 以45%的产率得到(R)-4-溴-1,2-环氧基丁烷
  参考文献：
  名称：

  Predictable Stereoselective and Chemoselective Hydroxylations and Epoxidations with P450 3A4

  摘要：

  Enantioselective hydroxylation of one specific methylene in the presence of many similar groups is debatably the most challenging chemical transformation. Although chemists have recently made progress toward the hydroxylation of inactivated C-H bonds, enzymes such as P450s (CYPs) remain unsurpassed in specificity and scope. The substrate promiscuity of many P450s is desirable for synthetic applications; however, the inability to predict the products of these enzymatic reactions is impeding advancement. We demonstrate here the utility of a chemical auxiliary to control the selectivity of CYP3A4 reactions. When linked to substrates, inexpensive, achiral theobromine directs the reaction to produce hydroxylation or epoxidation at the fourth carbon from the auxiliary with pro-R facial selectivity. This strategy provides a versatile yet controllable system for regio-, chemo-, and stereoselective oxidations at inactivated C-H bonds and demonstrates the utility of chemical auxiliaries to mediate the activity of highly promiscuous enzymes.

  DOI：

  10.1021/ja200551y

文献信息

• Total Synthesis and Biological Evaluation of Halipeptins A and D and Analogues
  作者：K. C. Nicolaou、Dimitrios E. Lizos、David W. Kim、Daniel Schlawe、Rita G. de Noronha、Deborah A. Longbottom、Manuela Rodriquez、Mariarosaria Bucci、Giuseppe Cirino

  DOI：10.1021/ja060064v

  日期：2006.4.5

  macrolactamization led to a mixture of halipeptins A (1a) and D (1d) and their analogues 3a, 3d (epimers at the indicated site) and 4a, 4d (epimers at the indicated site). The same route starting with D-Ala resulted in the exclusive formation of the epimeric halipeptin D analogue 3d. The synthesized halipeptins, together with the previously constructed oxazoline analogues 5d and 6d, were subjected to biological

  海洋衍生的 halipeptins A (1a) 和 D (1d) 及其类似物 3a、3d 和 4a、4d 是从构建块 10、13、14a 或 14d、15 和 16 开始合成的。 组装建筑物的第一个策略块，涉及大环内酰胺化反应形成 16 元环羟基硫代酰胺 52d 作为前体，提供了 halipeptin D 的表异亮氨酸类似物 (4d)，而第二种方法涉及在大环内酰胺化之前形成噻唑啉，导致 halipeptins A 的混合物(1a) 和 D (1d) 及其类似物 3a、3d（指定位点的差向异构体）和 4a、4d（指定位点的差向异构体）。以 D-Ala 开始的相同途径导致差向异构 halipeptin D 类似物 3d 的独家形成。合成的 halipeptins，连同先前构建的恶唑啉类似物 5d 和 6d，
• Doppelt und dreifach funktionalisierte, enantiomerenreine C₄-Synthesebausteine aus β-Hydroxybuttersäure, Äpfelsäure und Weinsäure
  作者：Ernst Hungerbühler、Dieter Seebach、Daniel Wasmuth

  DOI：10.1002/hlca.19810640523

  日期：1981.7.22

  Enantiomerically Pure Synthetic Building Blocks with Four C-Atoms and Two or Three Functional Groups from β-Hydroxy-butanoic, Malic, and Tartaric Acid

  具有四个C原子和两个或三个来自β-羟基丁酸，苹果酸和酒石酸的官能团的对映体纯合成构件
• Synthese optisch aktiver 2-Methyl- und 2-Äthyl-1, 6-dioxaspiro [4.4]-nonan- und -[4.5]decan-Pheromone aus einem gemeinsamen chiralen Vorläufer
  作者：Ernst Hungerbühler、Reto Naef、Daniel Wasmuth、Dieter Seebach、Hans-Rudolf Loosli、Adolf Wehrli

  DOI：10.1002/hlca.19800630724

  日期：1980.10.29

  Synthesis of Optically Active 2-Methyl- and 2-Ethyl-1, 6-dioxaspiro [4.4]nonane- and -[4.5]decane Pheromones from a Common Chiral Precursor

  从一个常见的手性前体合成旋光的2-甲基-和2-乙基-1，6-二氧杂螺[4.4]壬烷和-[4.5]癸烷信息素
• A Highly Efficient Asymmetric Synthesis of Vernakalant
  作者：John Limanto、Eric R. Ashley、Jingjun Yin、Gregory L. Beutner、Brendan T. Grau、Amude M. Kassim、Mary M. Kim、Artis Klapars、Zhijian Liu、Hallena R. Strotman、Matthew D. Truppo

  DOI：10.1021/ol501002a

  日期：2014.5.16

  transformations involve (1) an efficient zinc-amine-promoted etherification, (2) a highly stereoselective enzyme-catalyzed dynamic asymmetric transamination to set up the two contiguous chiral centers in the cyclohexane ring, and (3) a pyrrolidine ring formation via alkyl-B(OH)2-catalyzed amidation and subsequent imide reduction.

  描述了vernakalant的新型合成。使用廉价且容易获得的试剂，关键的转化涉及（1）有效的锌胺促进的醚化反应;（2）高度立体选择性的酶催化的动态不对称氨基转移，以在环己烷环中建立两个连续的手性中心，以及（ 3）经由烷基-B（OH）2催化的酰胺化和随后的酰亚胺还原形成吡咯烷环。
• Stereoselective total synthesis of (−)-pyrenophorin
  作者：Perugu Edukondalu、Reddymasu Sreenivasulu、Rudraraju Ramesh Raju

  DOI：10.1007/s11696-020-01132-2

  日期：2020.9

  AbstractStereoselective total synthesis of (−)-pyrenophorin was accomplished from commercially available starting material 2-bromo epoxide using regioselective ring opening and the intermolecular Mitsunobu cyclization as key steps. Graphic abstract

  摘要使用区域选择性的开环和分子间的Mitsunobu环化作为关键步骤，从市售的起始原料2-溴环氧化物中完成（-）-pyrenophorin的立体选择性全合成。 图形摘要