methaneselenenyl bromide | 73501-41-4

• 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: methaneselenenyl bromide
• 英文别名: methylselenyl bromide；methaneselenyl bromide；methyl selenohypobromite
• CAS: 73501-41-4
• 化学式: CH₃BrSe
• 分子量: 173.899
• InChiKey: PKIMGOOGSQUUIE-UHFFFAOYSA-N

物化性质

• 沸点：
  112.9±23.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.05
• 重原子数：
  3
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  L-半胱氨酸 、 methaneselenenyl bromide 在 氢氧化钾 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.25h， 以71%的产率得到S-(methylseleno)cysteine
  参考文献：
  名称：

  Identification and Synthesis of a Novel Selenium−Sulfur Amino Acid Found in Selenized Yeast:  Rapid Indirect Detection NMR Methods for Characterizing Low-Level Organoselenium Compounds in Complex Matrices

  摘要：

  After proteolytic digestion, aqueous extraction, and derivatization with diethyl pyrocarbonate or ethyl chloroformate, HPI-C-incluctively coupled plasma (ICP)-MS, GC-atomic emission detection (AED), and GC-MS analysis of high-selenium yeast stored at room temperature for more than 10 years showed selenomethionine as the major Se product along with substantial amounts of selenomethionine selenoxide hydrate and the previously unreported selenoamino acid having a Se-S bond, S(methylseleno)cysteine. The identity of the latter compound was confirmed by synthesis. The natural product was shown to be different from a synthetic sample of the isomeric compound Se-(methylthio)selenocysteine. Selenium-specific NMR spectroscopic methods were developed to directly analyze the aqueous extracts of the hydrolyzed selenized yeast without derivatization or separation. Selenomethionine and S-(methylseleno)cysteine were identified by Se-77-H-1 HMQC-TOCSY experiments.

  DOI：

  10.1021/jf049887z
• 作为产物：
  描述：

  二甲基二硒醚 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 methaneselenenyl bromide
  参考文献：
  名称：

  在无金属和无过氧化物条件下轻松合成含硒环戊烯的自由基加成/环化和硒基团转移策略

  摘要：

  开发了一种高度原子经济的分子间自由基加成/环化和硒基转移策略，用于在无金属和无过氧化物条件下有效合成含硒环戊烯。

  DOI：

  10.1002/chem.202103334

文献信息

• Stereo- and Chemo-Selectivity in Reduction of<i>α</i>-[Phenyl(or Methyl)seleno]alkyl Aryl Ketones with Metal Hydrides
  作者：Ikuo Aoki、Yoshiaki Nishibayashi、Sakae Uemura

  DOI：10.1246/bcsj.68.337

  日期：1995.1

  Metal hydride reduction of a variety of α-[phenyl(or methyl)seleno]alkyl aryl ketones gives a mixture of threo- and erythro-β-aryl-β-hydroxyalkyl phenyl(or methyl)selenides by carbonyl reduction and 1-aryl-1-alkanol by the substitution of a phenyl(or methyl)seleno group with hydrogen. With all metal hydrides examined the formation of the threo-isomer always predominated. The addition of various metal

  各种 α-[苯基（或甲基）硒基] 烷基芳基酮的金属氢化物还原反应通过羰基还原和 1-芳基还原得到苏-和赤-β-芳基-β-羟烷基苯基（或甲基）硒化物的混合物通过用氢取代苯基（或甲基）硒基而得到 1-烷醇。对于所有金属氢化物，苏式异构体的形成总是占主导地位。在还原系统中添加各种金属氯化物对非对映选择性影响不大，与迄今为止已知的各种 α-杂原子（N、P、O、S）取代酮的还原形成鲜明对比。
• First Example of Highly Stereoselective Synthesis of 1,2,3-Trisubstituted Cyclopropanes via Chiral Selenonium Ylides
  作者：Hai-Yang Wang、Fei Yang、Xin-Liang Li、Xue-Ming Yan、Zhi-Zhen Huang

  DOI：10.1002/chem.200801936

  日期：2009.4.6

  A new strategy for the highly stereoselective synthesis of three stereoisomers of chiral 1,2,3‐trisubstituted cyclopropanes in good yields with excellent diastereoselectivities and very high enantioselectivities (up to >99 % ee) was developed via selenonium ylides (see scheme). Possible pathways for the asymmetric cyclopropanations were also proposed.

  通过硒化叶立德开发了一种新的策略，该策略以高收率，极好的非对映选择性和极高的对映选择性（高达> 99％ee）（见方案），以高收率选择性合成了手性1,2,3-三取代环丙烷的三种立体异构体。还提出了不对称环丙烷化的可能途径。
• Captodative substituent effects XXI.
  作者：S. Piettre、Z. Janousek、R. Merenyi、H.G. Viehe

  DOI：10.1016/s0040-4020(01)96649-9

  日期：1985.1

  reacts more slowly, producing mainly the α-selenenyl adduct. Dehydrohalogenation of adducts provides a general and valuable method for the preparation of olefins carrying methyl or phenylselenenyl groups in α-position to electron-withdrawing substituents.

  在不同极性的溶剂中，可将甲烷和苯硒烯基溴化物或氯化物和苯亚磺酰氯加到被吸电子基团取代的碳-碳双键上。通常形成两个区域异构体加合物和和或和，可以通过在回流的乙腈中平衡来相互转化。机械上感兴趣的是，区域异构体也可以衍生自亚硒基三卤化物加合物。与丙烯酸酯相比，丙酸酯的反应更慢，主要产生α-硒烯加合物。加合物的脱卤化氢为制备在α-位带有吸电子取代基的甲基或苯基硒烯基的烯烃提供了一种通用且有价值的方法。
• A Stereoselective Route to (E)-1-Alkylseleno-1-Alkenes via Hydroboration-Iodination of Terminal Alkylselenoacetylenes with Dicyclohexylborane
  作者：De-Yu Yang、Xian Huang

  DOI：10.1080/00397919708005022

  日期：1997.1

  (E)-1-Alkylseleno-1-alkenes 4 have been synthesized with high stereoselectivity by hydroboration-iodination of terminal alkylselenoactylenes with dicyclohexylborane.

  (G)-1-甲基三烯二硒烷烃4通过水化物-碘化物方法合成具有很高的立体选择性。
• Captodative substituent effects — Part XXXI olefins with captodative substitution in [2+2] cycloadditions
  作者：Ch. De Cock、S. Piettre、F. Lahousse、Z. Janousek、R. Merényi、H.G. Viehe

  DOI：10.1016/s0040-4020(01)97193-5

  日期：1985.1

  Olefins with captodative substitution are excellent partners in [2+2] cycloadditions leading to cyclobutane derivatives. The reaction rates increase with the radical stabilising power of the substituents. Thio- and selenoalkyl(aryl) substituted gemdifluoroolefins allow the synthesis of new cyclobutane derivatives.

  具有Capdativeative取代的烯烃是导致环丁烷衍生物的[2 + 2]环加成反应的极好伙伴。反应速率随取代基的自由基稳定能力而增加。硫代和硒代烷基（芳基）取代的宝石二氟烯烃可以合成新的环丁烷衍生物。