2-丁烯,1-溴-3-碘-,(2Z)- | 149220-27-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机碘化物
• 中文名称: 2-丁烯,1-溴-3-碘-,(2Z)-
• 英文名称: (Z)-1-bromo-3-iodo-2-butene
• 英文别名: (Z)-1-bromo-3-iodo-but-2-ene；(Z)-1-bromo-3-iodobut-2-ene
• CAS: 149220-27-9
• 化学式: C₄H₆BrI
• 分子量: 260.9
• InChiKey: SCLKMDCLTRILPY-RQOWECAXSA-N

物化性质

• 沸点：
  193.5±23.0 °C(Predicted)
• 密度：
  2.174±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  2-丁烯,1-溴-3-碘-,(2Z)- 、 6-benzyl-3-isobutoxycyclohex-2-en-1-one 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 以79%的产率得到6-benzyl-6-((Z)-3-iodobut-2-en-1-yl)-3-isobutoxycyclohex-2-en-1-one
  参考文献：
  名称：

  Intramolecular Conjugate Addition of Alkenyl and Aryl Functions to Enones Initiated by Lithium−Iodine Exchange

  摘要：

  [GRAPHICS]Treatment of each of the substrates 20-26, 29, and 46-48 with t-BuLi in THF, in the presence of HMPA and TMSCl, provides good-to-excel lent yields of the intramolecular conjugate addition products 30-36, 37, and 49-51, respectively.

  DOI：

  10.1021/ol016288u
• 作为产物：
  描述：

  Methanesulfonic acid (Z)-3-iodo-but-2-enyl ester 在 lithium bromide 作用下， 以 丙酮 为溶剂， 反应 0.42h， 生成 2-丁烯,1-溴-3-碘-,(2Z)-
  参考文献：
  名称：

  Studies Directed toward the Total Synthesis of Cerorubenic Acid-III. 4. Exploration of an Organometallic Approach to Construction of the Eastern Sector

  摘要：

  The concept of an intramolecular organometallic approach to the most illustrious member of the cerorubenic acid family is outlined. Alkylation of ketone 2 with the ethyl iodoacetate and conversion of the resultant intermediate into lactone 9 provided a ready means for attaching side chains carrying a vinyl iodide substituent. Arrival at the key iodo ketones was next realized by a three-step sequence involving sodium borohydride reduction, regiocontrolled silylation of the primary hydroxyl group in the diol, and Dess-Martin oxidation. The crucial six-membered cyclization of these intermediates is not favored kinetically, and reductive deiodination was observed, if reaction occurred at all. Attempts to generate vinyl stannanes from these same substrates were also ineffective. The failure of this approach demonstrates the difficulties associated with closure of ring D, a phenomenon that has earlier been observed in the context of other exploratory routes to cerorubenic acid-III.

  DOI：

  10.1021/jo00120a026

文献信息

• Carbopalladation of Nitriles:  Synthesis of Benzocyclic Ketones and Cyclopentenones via Pd-Catalyzed Cyclization of ω-(2-Iodoaryl)alkanenitriles and Related Compounds
  作者：Alexandre A. Pletnev、Richard C. Larock

  DOI：10.1021/jo0262006

  日期：2002.12.1

  An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.

  已经开发出一种通过腈的分子内碳弹头化合成2，2-二取代的苯并环酮的有效方法。取代的3-（2-碘芳基）丙烷腈的环化以高收率提供茚满酮。该反应与多种官能团相容。该方法已经扩展到四氢萘酮和环戊烯酮的合成。
• Evolution of an oxidative dearomatization enabled total synthesis of vinigrol
  作者：Qingliang Yang、Cristian Draghici、Jon T. Njardarson、Fang Li、Brandon R. Smith、Pradipta Das

  DOI：10.1039/c3ob42191k

  日期：——

  synthetic strategy resulting in a total synthesis of vinigrol is presented. Oxidative dearomatization/intramolecular Diels–Alder cycloaddition has served as the successful cornerstone for all of the approaches. Extensive radical cyclization efforts to form the tetracyclic core resulted in interesting and surprising reaction outcomes, none of which could be advanced to vinigrol. These cyclization obstacles

  介绍了导致vinigrol全合成的合成策略的演变。氧化脱芳构化/分子内 Diels-Alder 环加成已成为所有方法的成功基石。形成四环核心的广泛自由基环化努力导致了有趣且令人惊讶的反应结果，其中没有一个可以推进到vinigrol。通过使用 Heck 而不是自由基环化成功地克服了这些环化障碍。全合成的特点是三氟乙醚保护基团首次用于有机合成。除了保护 C8a 羟基之外，还介绍了它的选择逻辑和基团的重要性，并讨论了去除它的策略。由于紧凑的四环笼，该路线是围绕许多不寻常的反应观察建立的，并且已经出现了解决方案。例如，首次发现了具有三氟乙基离去基团的 Grob 断裂反应，观察到有趣的二氧化硒烯丙基氧化中断，以及有趣的催化剂和抗衡离子依赖性定向氢化。
• Rapid Assembly of Vinigrol’s Unique Carbocyclic Skeleton
  作者：Jason G. M. Morton、Cristian Draghici、Laura D. Kwon、Jon T. Njardarson

  DOI：10.1021/ol901519k

  日期：2009.10.15

  Detailed in this account are our efforts toward the total synthesis of vinigrol. A highly expedient and convergent synthetic approach made possible by the use of a strategic oxidative dearomatization reaction coupled with a series of ensuing substrate controlled transformations is discussed.

  在这个帐户中详细介绍了我们对vinigrol 全合成所做的努力。讨论了一种非常方便和收敛的合成方法，该方法通过使用战略性氧化脱芳构化反应以及一系列随后的底物控制转化而成为可能。
• Remarkable template effect of a Lewis acid receptor in the intramolecular radical cyclization: control of reaction pathway as well as stereochemistry
  作者：Takashi Ooi、Yasutoshi Hokke、Eiji Tayama、Keiji Maruoka

  DOI：10.1016/s0040-4020(00)01007-3

  日期：2001.1

  Abstract A remarkable template effect in the intramolecular radical cyclization process has been observed by the successful utilization of Lewis acid receptor, aluminum tris(2,6-diphenylphenoxide) (ATPH). The origin of this efficient template effect by ATPH would be ascribable to the well-defined reaction environment created in front of the aluminum coordination center; this enables appropriate proximity

  摘要 通过路易斯酸受体三(2,6-二苯酚)铝(ATPH)的成功利用，观察到分子内自由基环化过程中的显着模板效应。ATPH 产生的这种有效模板效应可归因于在铝配位中心前创造的明确的反应环境；这使得初始产生的碳自由基与过渡态的不饱和碳-碳键适当接近，以实现平滑环化，因此完全抑制了不希望的分子间还原途径。此外，ATPH 独特的空腔提供的这种构象限制改变了环化的立体选择性。
• Chiral 1,2,3‐Triazolium Salt Catalyzed Asymmetric Mono‐ and Dialkylation of 2,5‐Diketopiperazines with the Construction of Tetrasubstituted Carbon Centers
  作者：Ju‐Song Yang、Ka Lu、Chen‐Xiao Li、Zu‐Hang Zhao、Xiao‐Ming Zhang、Fu‐Min Zhang、Yong‐Qiang Tu

  DOI：10.1002/anie.202114129

  日期：2022.2.21

  Chiral spirocyclic-amide-derived triazolium salts were used as new phase-transfer organocatalysts for asymmetric alkylation to construct 2,5-diketopiperazine motifs containing one or two tetrasubstituted carbon centers in high yields with excellent cis-diastereoselectivity and enantioselectivity. Control experiments and DFT calculations revealed the possible reaction mechanism and the origins of the

  手性螺环酰胺衍生的三唑鎓盐被用作不对称烷基化的新型相转移有机催化剂，以高产率构建含有一个或两个四取代碳中心的 2,5-二酮哌嗪基序，具有优异的顺式-非对映选择性和对映选择性。对照实验和 DFT 计算揭示了可能的反应机理和异常非对映选择性和对映选择性的起源。