cis-3,4-bis(mesyloxymethyl)-1-cyclobutene | 185119-53-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: cis-3,4-bis(mesyloxymethyl)-1-cyclobutene
• 英文别名: (cis-Cyclobut-3-ene-1,2-diyl)bis(methylene) dimethanesulfonate；[(1R,4S)-4-(methylsulfonyloxymethyl)cyclobut-2-en-1-yl]methyl methanesulfonate
• CAS: 185119-53-3
• 化学式: C₈H₁₄O₆S₂
• 分子量: 270.328
• InChiKey: WHVNYGHISMWTJA-OCAPTIKFSA-N

物化性质

• 沸点：
  482.1±18.0 °C(Predicted)
• 密度：
  1.391±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  cis-3,4-bis(mesyloxymethyl)-1-cyclobutene 在 lithium aluminium tetrahydride 作用下， 以 various solvent(s) 为溶剂， 反应 23.0h， 生成 cis-3,4-dimethyl-1-cyclobutene
  参考文献：
  名称：

  High selectivities in electrophilic additions to cyclobutene compounds

  摘要：

  Epoxidation of 2, 3, 4 with m-CPBA mainly led to the cis-attack products whereas 1 and 6 led to the other selectivity. The result was reversed, from 4, with Payne's reagent Bromohydroxylation of 4 involved an intermediate bromonium ion syn to the substituents. Haloselenylations occurred with the syn-selectivity from 1, 2, 3 and 4, to the anti-selectivity from 6, and without selectivity from 5. NOE enhancement measurements and several chemical correlations led to the stereochemical assignments. Formation of the intramolecular reaction products 24 and 25 was also pointed out. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/s0040-4020(96)00945-3
• 作为产物：
  描述：

  cis-3-cyclobutene-1,2-dicarboxylic anhydride 在 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 cis-3,4-bis(mesyloxymethyl)-1-cyclobutene
  参考文献：
  名称：

  2-氮杂双环[2.1.1]己烷的新合成。

  摘要：

  从顺式-环丁-3-烯-1,2-二羧酸酐7开始，已经完成了2-氮杂双环[2.1.1]己烷环系统的有效合成，该顺式-环丁-3-烯-1,2-二羧酸酐是使用光化学方法制备的。该新策略的关键步骤涉及将苯硒基溴化物立体选择性地亲电子加成至衍生自7的环丁二氨基甲酸酯16的双键。随后在氢化钠存在下17a的闭环反应使2-氮杂双环己烷化合物18具有令人满意的总体让。还原性除去苯基硒烯基并随后脱保护，迅速导致在碳环上官能化的氨基衍生物4a。然后从中间体二磺酰胺23合成羟基和羧酸衍生物4b，c。在另外三个步骤之后，用乙酸钾置换活化的氨基，得到羟基衍生物4b。最后，在琼斯条件下氧化4b的醇官能团，然后进行氢解，得到羧酸衍生物4c，它是2,4-methanoproline 1的第一个报道的β-异构体。

  DOI：

  10.1021/jo001790y

文献信息

• Stereoselective epoxidation of cis-3,4-disubstituted-(CH2X)-cyclobutenes with dimethyldioxirane and peroxy acids. Experimental and computational evidence for a syn-orienting electrostatic effect
  作者：Mauro Freccero、Remo Gandolfi、Mirko Sarzi-Amadè

  DOI：10.1016/s0040-4020(99)00630-4

  日期：1999.9

  The epoxidation reactions of a series of cis-3,4-disustituted-(CH2X)-cyclobutenes 1–8 with dimethyldioxirane (DMD) and mClPBA have been investigated with both reagents. A remarkable syn diastereoselectivity in the formation of the epoxide has been observed for substrates bearing electron withdrawing substituents. Transition structures for epoxidations of 3,4-dimethylcyclobutene (1), diastereoisomeric

  两种试剂都研究了一系列顺式3,4-取代的（CH 2 X）-环丁烯1-8与二甲基二环氧乙烷（DMD）和mClPBA的环氧化反应。对于带有吸电子取代基的底物，在环氧化物的形成中观察到了显着的非对映选择性。3,4-二甲基环丁烯（1），非对映异构体3,5-二氧杂-4-硫杂-双环[5.2.0]非-8-烯-4-氧化物7和8以及3,4-bis的环氧化过渡结构（甲氧甲基）-1-环丁烯（5）已使用B3LYP / 6–31G *方法定位了具有二环氧乙烷和过氧甲酸的溶液。主要由于对氧化剂的过氧氧与烯烃的带正电荷的均烯丙基氢发生静电吸引相互作用，因此使实验性的主要合成面部选择性合理化。
• An Orthogonal Modular Approach to Macromonomers Using Clickable Cyclobutenyl Derivatives and RAFT Polymerization
  作者：Dao Le、Véronique Montembault、Sagrario Pascual、Stéphanie Legoupy、Laurent Fontaine

  DOI：10.1021/ma3016163

  日期：2012.10.9

  mediate the RAFT polymerization of ethyl acrylate and N-isopropylacrylamide. Well-defined polymers with controlled molecular weights (Mn = 3700–11 500 g·mol–1) and narrow molecular weight distributions (PDI = 1.06–1.14) were thus obtained that retain the cyclobutene functionality, demonstrating the orthogonality of the RAFT process toward the cyclobutenyl insaturation. Combination of CuACC and RAFT polymerization

  衍生自单甲醚聚环氧乙烷（PEO），聚丙烯酸乙酯（PEA），聚N-异丙基丙烯酰胺（PNIPAM）和PEO- b的一系列基于环丁烯的大分子单体-PNIPAM是通过“点击”铜催化的叠氮化物-炔烃环加成（CuAAC）和可逆加成-断裂链转移（RAFT）聚合反应合成的。首先，成功地获得了具有叠氮基，炔烃和/或链转移剂的原始二官能和三官能环丁烯前体，并对其进行了充分表征。然后将叠氮基和炔基官能化的环丁烯与带有叠氮基或炔基的改性PEO偶联，从而产生定量环化的基于环丁烯的PEO，如NMR光谱法和MALDI-TOF质谱法所确定的。新的链转移剂封端的环丁烯用于介导丙烯酸乙酯和N-异丙基丙烯酰胺的RAFT聚合。分子量可控的定义明确的聚合物（M n= 3700–11 500 g·mol –1）和窄分子量分布（PDI = 1.06-1.14），因此保留了环丁烯官能度，证明了RAFT过程对环丁烯基不饱和度的正交性。使用
• An Efficient Synthesis of 3,3′-Bipiperidines Using an ROM/RCM Metathesis Sequence: Extension to Oxygenated Analogues
  作者：Jacques Lebreton、Stéphanie Legoupy、Esma Maougal、Sylvain Dalençon、Morwenna Pearson-Long、Monique Mathé-Allainmat

  DOI：10.1055/s-0034-1378663

  日期：——

  A short and efficient diastereoselective synthesis of 3,3-bipiperidine and 3,3-bis(1,2,3,6-tetrahydropyridine) was accomplished using a tandem ring-opening metathesis/ring-closing metathesis (ROM/RCM) sequence as a key step. This strategy has been extended to the synthesis of the oxygenated analogues.
• A New Synthesis of 2-Azabicyclo[2.1.1]hexanes
  作者：Cyrille Lescop、Laurence Mévellec、François Huet

  DOI：10.1021/jo001790y

  日期：2001.6.1

  An efficient synthesis of the 2-azabicyclo[2.1.1]hexane ring system has been accomplished starting from cis-cyclobut-3-ene-1,2-dicarboxylic anhydride 7, which was prepared using a photochemical method. The key step of this new strategy involved a stereoselective electrophilic addition of phenylselenyl bromide to the double bond of cyclobutene dicarbamate 16 derived from 7. The subsequent ring closure

  从顺式-环丁-3-烯-1,2-二羧酸酐7开始，已经完成了2-氮杂双环[2.1.1]己烷环系统的有效合成，该顺式-环丁-3-烯-1,2-二羧酸酐是使用光化学方法制备的。该新策略的关键步骤涉及将苯硒基溴化物立体选择性地亲电子加成至衍生自7的环丁二氨基甲酸酯16的双键。随后在氢化钠存在下17a的闭环反应使2-氮杂双环己烷化合物18具有令人满意的总体让。还原性除去苯基硒烯基并随后脱保护，迅速导致在碳环上官能化的氨基衍生物4a。然后从中间体二磺酰胺23合成羟基和羧酸衍生物4b，c。在另外三个步骤之后，用乙酸钾置换活化的氨基，得到羟基衍生物4b。最后，在琼斯条件下氧化4b的醇官能团，然后进行氢解，得到羧酸衍生物4c，它是2,4-methanoproline 1的第一个报道的β-异构体。
• High selectivities in electrophilic additions to cyclobutene compounds
  作者：Laurence Mévellec、Michel Evers、François Huet

  DOI：10.1016/s0040-4020(96)00945-3

  日期：1996.11

  Epoxidation of 2, 3, 4 with m-CPBA mainly led to the cis-attack products whereas 1 and 6 led to the other selectivity. The result was reversed, from 4, with Payne's reagent Bromohydroxylation of 4 involved an intermediate bromonium ion syn to the substituents. Haloselenylations occurred with the syn-selectivity from 1, 2, 3 and 4, to the anti-selectivity from 6, and without selectivity from 5. NOE enhancement measurements and several chemical correlations led to the stereochemical assignments. Formation of the intramolecular reaction products 24 and 25 was also pointed out. Copyright (C) 1996 Elsevier Science Ltd