(Z)-2-(iodomethylidene)-4-penten-1-ol | 70396-09-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2-(iodomethylidene)-4-penten-1-ol
• 英文别名: (Z)-2-(iodomethylidene)-4-penten-4-ol；(Z)-2-iodomethylene-pent-4-en-1-ol；(2Z)-2-(iodomethylidene)pent-4-en-1-ol
• CAS: 70396-09-7
• 化学式: C₆H₉IO
• 分子量: 224.041
• InChiKey: FXFVVQJFUOLILS-XQRVVYSFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-2-(iodomethylidene)-4-penten-1-ol 在 叔丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 10.5h， 生成 (Z)-1-methoxy-2-<(trimethylsilyl)methylidene>-4-pentene
  参考文献：
  名称：

  Reactivity of allylic dimetallic zinc reagents. 1

  摘要：

  Allylic 1,1-dimetallic species 2, prepared in situ from the propargylic ether 1, are multicoupling reagents. They were allowed to react in a one-pot maction, with a large variety of electrophiles E1-carbonyl compounds (acyl chlorides, aldehydes, ketones, phenyl isocyanate, methyl chloroformate), alkyl bromides, and an amino ether-and then E2-acidic water, iodine, aryl or vinyl iodide in the presence of palladium(0). The isolated yields, based on 1 (5 steps), are fair to good in most cases. The first attack (E1) always occurs on the carbon atom alpha to the oxygen; the second attack (E2) is regio- and stereoselective on the carbon atom a to the TMS moiety.

  DOI：

  10.1021/jo00051a042
• 作为产物：
  描述：

  2-丙炔-1-醇 、 烯丙基溴化镁 生成 (Z)-2-(iodomethylidene)-4-penten-1-ol
  参考文献：
  名称：

  格利雅乙烯基反应混合物γ化合物：II.。碘醇的烷基化和芳基化

  摘要：

  γ-官能取代的乙烯基格氏试剂的碘化，是通过将有机镁化合物添加到α-亚油酸或α-烯醇中而制得的，碘化立体定向。在（PPh 3）2 NiCl 2存在下用格氏试剂处理这些碘化物，得到烯丙基醇。该反应以高的立体选择性进行。

  DOI：

  10.1016/s0022-328x(00)83278-7

文献信息

• Domino Sequences Involving Stereoselective Hydrazone-Type Heck Reaction and Denitrogenative [1,5]-Sigmatropic Rearrangement
  作者：Shuling Yu、Lijin Zhou、Sihan Ye、Xiaofeng Tong

  DOI：10.1021/jacs.3c01075

  日期：——

  via an acid-promoted condensation. A key strategic advantage of this Heck paradigm is that the resultant Heck product allylic diazene rapidly undergoes stereospecific denitrogenative [1,5]-sigmatropic rearrangement, eventually furnishing a domino sequence toward 3-substituted tetrahydropyridine (THP) with high enantioselectivity. The substrate-induced diastereoselective version has also been realized

  尽管烯烃伙伴与各种亲电试剂的 Heck 反应取得了巨大成功，但以碳═杂原子对应物为中心的变体仍然难以捉摸。在此，我们报道了N -[( Z )-3-碘代烯丙基]-氨基乙醛和水合肼 (NH 2 NH 2 –H 2)的 Pd(0) 催化的不对称分子内腙型 Heck 反应O), 其中所需的腙是通过酸促进的缩合原位生成的。这种 Heck 范式的一个关键战略优势是生成的 Heck 产物烯丙基二氮迅速经历立体特异性脱氮 [1,5]-sigmatropic 重排，最终为具有高对映选择性的 3-取代四氢吡啶 (THP) 提供多米诺骨牌序列。底物诱导的非对映选择性版本也已实现，专门提供顺式-2,5-二取代 THP。该序列的实用性通过多个有价值的生物活性靶标的正式合成得到证明，包括 3-乙基吲哚喹啉、preclamol 和 niraparib。
• Synthesis of Pyrroles through Coupling of Enyne-hydrazones with Fischer Carbene Complexes
  作者：Yanshi Zhang、James W. Herndon

  DOI：10.1021/ol034414j

  日期：2003.6.1

  The coupling of enyne-imines with Fischer carbene complexes leads to the formation of alkenylpyrrole derivatives. Maximum yields of pyrrole adducts were obtained using N,N-dimethylhydrazones. A mechanism involving alkyne insertion followed by nucleophilic attack of the imine nitrogen at the intermediate alkenylcarbene complex was proposed.
• Synthesis of benzofurans through coupling of dienylacetylenes with carbene complexes: total synthesis of egonol
  作者：Jianwei Zhang、Yi Zhang、Yanshi Zhang、James W Herndon

  DOI：10.1016/s0040-4020(03)00823-8

  日期：2003.7

  The reaction of various carbene complexes with dienylacetylenes has been examined. The reaction has been used as the cornerstone for the preparation of the nor-neolignan natural product egonol in five steps from readily available components. In most examples of the carbene-alkyne coupling, the reaction proceeds to form benzofuran derivatives. In the case of one highly functionalized terminal alkyne, a competing rearrangement/cyclization process occurs in preference to the carbene coupling process. The use of silylated alkynes subverts this process. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Liang, Guangxin; Seiple, Ian B.; Trauner, Dirk, Organic Letters, 2005, vol. 7, # 14, p. 2836 - 2839
  作者：Liang, Guangxin、Seiple, Ian B.、Trauner, Dirk

  DOI：——

  日期：——
• DUBOUDIN J. G.; JOUSSEAUME B.; BONAKDAR A.; SAUX A., J. ORGANOMETAL. CHEM., 1979, 168, NO 2, 227-232
  作者：DUBOUDIN J. G.、 JOUSSEAUME B.、 BONAKDAR A.、 SAUX A.

  DOI：——

  日期：——