(S,E)-5-iodo-4-methylpent-4-ene-1,2-diol | 948837-47-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (S,E)-5-iodo-4-methylpent-4-ene-1,2-diol
• 英文别名: (E,2S)-5-iodo-4-methylpent-4-ene-1,2-diol
• CAS: 948837-47-6
• 化学式: C₆H₁₁IO₂
• 分子量: 242.057
• InChiKey: QLQNUZMXCHCJMC-QVQDZQDPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S,E)-5-iodo-4-methylpent-4-ene-1,2-diol 在 咪唑 、 1,3-丙二硫醇 、 三氟化硼乙醚 、 叔丁基锂 、 对甲苯磺酸 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成
  参考文献：
  名称：

  萘基哌净全合成研究：通过环过Diels-Alder策略构建CDE环系统

  摘要：

  跨环的Diels–Alder（TADA）反应被用于合成nakiterpiosin（1）的CDE环系统。四环化合物25可能是1的总合成中的关键中间体。

  DOI：

  10.1016/j.tetlet.2007.05.174
• 作为产物：
  描述：

  (S)-pent-4-yne-1,2-diol 在 二氯二茂锆 、 三甲基铝 、 碘 作用下， 以 1,2-二氯乙烷 、 乙醚 为溶剂， 反应 41.75h， 以60%的产率得到(S,E)-5-iodo-4-methylpent-4-ene-1,2-diol
  参考文献：
  名称：

  Studies of the Synthesis of Providencin: Construction and Assembly of Two Major Subunits

  摘要：

  The "northern" sector of the cembranoid diterpene providencin containing a tetrasubstituted cyclobutane was synthesized from the bis(acetonide) of D-glucose using dicyclopentadienylzirconium(0)-mediated oxygen abstraction from a furanose. Oxidative scission of the vinyl substituent of this cyclobutane gave an aldehyde, which was reacted with an alkynylstannane to provide an allenol. Cyclization of the derived allenone with silver nitrate led to a cyclobutylfuran comprising the northern subunit of providencin. The "southern" sector of the cembranoid skeleton containing a trisubstituted iodoalkene attached to an alpha-phenylselenyl-gamma-lactone was synthesized from (R)-glycidol. Negishi carbometalation-iodination established the (E)-iodoalkene, and addition of the lithio dianion of phenylselenoacetic acid to a tosylate generated the substituted lactone. The two sectors were joined via stannylation of the furan of the northern component followed by Stille cross-coupling of the furylstannane with the iodoalkene of the southern subunit. Linkage of the two segments was also made at C12-C13 of providencin using intermolecular aldol condensation of the enolate from the selenyl lactone of the southern portion with an acetaldehyde appendage on the cyclobutane of the northern sector. Closure of the providencin macrocycle from these conjoined subunits was unsuccessful.

  DOI：

  10.1021/jo402485h

文献信息

• Enantioselective synthesis of aurisides A and B, cytotoxic macrolide glycosides of marine origin
  作者：Kiyotake Suenaga、Hiroshi Hoshino、Takanori Yoshii、Kazunori Mori、Hiroki Sone、Yuhki Bessho、Akira Sakakura、Ichiro Hayakawa、Kiyoyuki Yamada、Hideo Kigoshi

  DOI：10.1016/j.tet.2006.05.077

  日期：2006.8

  The enantioselective synthesis of aurisides A and B, macrolide glycosides of marine origin, was achieved by a convergent approach. The C1–C9 segment 4 was prepared from (R)-pantolactone, and the C10–C17 segment 14 was synthesized from (R)-glycidyl trityl ether. The Nozaki–Hiyama–Kishi reaction between 4 and 14 and subsequent reactions gave seco acid 10, which was converted into the aglycon (3) of aurisides

  通过收敛的方法实现了Aurisides A和B（海洋来源的大环内酯糖苷）的对映选择性合成。C1-C9段4由（R）-泛内酯制备，C10-C17段14由（R）-缩水甘油基三苯甲基醚合成。4至14之间的Nozaki–Hiyama–Kishi反应及随后的反应产生了癸二酸10，其通过构建14元内酯和溴取代的共轭二烯而转化为耳苷的糖苷（3）。糖苷配基的糖基化反应提供了苷A和B.
• Studies toward the Synthesis of an Oxazole-Based Analog of (−)-Zampanolide
  作者：Christian P. Bold、Cindy Klaus、Bernhard Pfeiffer、Jasmine Schürmann、Rafael Lombardi、Daniel Lucena-Agell、J. Fernando Díaz、Karl-Heinz Altmann

  DOI：10.1021/acs.orglett.1c00378

  日期：2021.3.19

  Studies are described toward the synthesis of an oxazole-based analog of (−)-zampanolide (2). Construction of (−)-dactylolide analog 22 was achieved via alcohol 5 and acid 4 through esterification and Horner–Wadsworth–Emmons (HWE)-based macrocyclization; however, attempts to attach (Z,E)-sorbamide to 22 proved unsuccessful. The C(8)–C(9) double bond of the macrocycle was prone to migration into conjugation

  已经描述了关于合成基于恶唑的（-）-扎曼醇化物（2）的类似物的研究。通过酯化作用和基于霍纳-沃兹沃斯-埃蒙斯（HWE）的大环化反应，通过醇5和酸4来构建（-）-缩水甘油类似物22。但是，尝试将（Z，E）-山梨酰胺连接到22上的尝试未成功。大环的C（8）–C（9）双键易于迁移至与恶唑环共轭，这通常可能会限制具有芳香族部分的扎曼醇化物类似物作为四氢吡喃替代品的用途。
• Total Synthesis of (−)-Dactylolide and Formal Synthesis of (−)-Zampanolide via Target Oriented β-<i>C</i>-Glycoside Formation
  作者：Fei Ding、Michael P. Jennings

  DOI：10.1021/jo8009853

  日期：2008.8.1

  The total synthesis of (−)-dactylolide and formal synthesis of (−)-zampanolide via target oriented β-C-glycoside formation is described. The two key reactions involved a stereoselective reduction of the appropriate oxocarbenium cation and a highly chemo- and diastereoselective ring-closing metathesis protocol for the formation of the macrocyclic core. In addition to the described chemistry, in vitro

  描述了通过靶标定向的β- C-糖苷形成的（-）-三羟甲基萘酚的全合成和（-）-zampanolide的形式合成。这两个关键反应涉及适当的氧碳鎓阳离子的立体选择性还原以及形成大环核心的高度化学和非对映选择性的闭环复分解方案。除上述化学方法外，针对NCI的60个癌细胞系进行了体外天然内酯的对映体筛选，有助于阐明N的至关重要性。扎曼醇化物的β-酰基半胱氨酸侧链，因其报道的强纳摩尔细胞毒性而被报道。此外，借助于（-）-聚乳酸的体外筛选，对于多种癌症，现在已经出现了有希望的癌症治疗先导。更具体地，（ - ） - dactylolide显示GI 50个在纳摩尔值（25-99毫微克/毫升）针对四种细胞系HL-60范围，K-562，HCC-2998和SF-539，同时显示适度的LC 50个值。
• A Transannular Diels-Alder Strategy to the Construction of the CDE Ring System of Nakiterpiosin
  作者：Hiroyoshi Takamura、Yuji Yamagami、Tomonori Ito、Masahiro Ito、Hirokazu Arimoto、Isao Kadota、Daisuke Uemura

  DOI：10.3987/com-08-s(f)26

  日期：——

  The transannular Diels-Alder (TADA) reaction was applied to the synthesis of the CDE ring system of nakiterpiosin (1). TADA product 28 is a key intermediate toward the total synthesis of 1.

  将跨环 Diels-Alder (TADA) 反应应用于 Nakiterpiosin (1) 的 CDE 环系统的合成。TADA 产物 28 是全合成 1 的关键中间体。
• Total synthesis of (+)-Z-deoxypukalide, a furanobutenolide-based cembranoid isolated from the pacific octocoral Leptogorgia spp.
  作者：Bencan Tang、Christopher D. Bray、Gerald Pattenden、Joseph Rogers

  DOI：10.1016/j.tet.2010.01.059

  日期：2010.3

  A total synthesis of (+)-Z-deoxypukalide 3 using a combination of Stille and Nozaki-Hiyama-Kishi(NHK) coupling reactions as key steps, is described. During this study a new practical synthesis of the substituted butenolide intermediate 10, based on a combination of RCM and CM reactions from the cyclobutene ester 21 in the presence of 2-methylpropenol was also developed. Attempts to apply the intramolecular NHK reaction to the substrates 8a and 8b containing an ester group adjacent to the reacting aldehyde functionality gave disappointing low yields (<6%) of the corresponding coupled products 9. The synthetic (+)-Z-deoxypukalide 3 was correlated with naturally derived material, and also with pukalide 1, the first member of the furanobutenolide-based cembranoids to be isolated from corals. (C) 2010 Elsevier Ltd. All rights reserved.