(4S)-4-[(tert-Butyldimethylsilyl)oxy]-2-iodocyclohex-2-en-1-one | 198407-83-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S)-4-[(tert-Butyldimethylsilyl)oxy]-2-iodocyclohex-2-en-1-one
• 英文别名: (S)-4-(tert-butyldimethylsilyloxy)-2-iodocyclohex-2-enone；(4S)-4-[tert-butyl(dimethyl)silyl]oxy-2-iodocyclohex-2-en-1-one
• CAS: 198407-83-9
• 化学式: C₁₂H₂₁IO₂Si
• 分子量: 352.288
• InChiKey: XWYHMUYXLHQPJJ-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.06
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S)-4-[(tert-Butyldimethylsilyl)oxy]-2-iodocyclohex-2-en-1-one 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 copper(l) iodide 、 三(2-呋喃基)膦 、 戴斯-马丁氧化剂 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 3-[2-[1-[tert-butyl(dimethyl)silyl]oxy-3-[(3S)-3-[tert-butyl(dimethyl)silyl]oxy-6-oxocyclohexen-1-yl]prop-2-ynyl]phenyl]prop-2-ynal
  参考文献：
  名称：

  First generation of the dienediyne portion of a dienediyne model of the neocarzinostatin chromophore by a McMurry reaction

  摘要：

  The first 3-->6 type ring-closing dienediyne synthesis by means of a McMurry reaction was realized by converting the ketoaldehyde 20 into the 6-/10-membered bicyclic dienediyne 22. Diastereoselective pinacol couplings 20-->23 and 21-->24 giving 6-/10-membered bicyclic enediynediols were possible, too. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)10010-7
• 作为产物：
  描述：

  3,4-O-isopropylidene-3(R),4(S)-dihydroxycyclohexanone 在 4-二甲氨基吡啶 、 sodium hydroxide 、 碘 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 吡啶 、 四氯化碳 、 二氯甲烷 为溶剂， 生成 (4S)-4-[(tert-Butyldimethylsilyl)oxy]-2-iodocyclohex-2-en-1-one
  参考文献：
  名称：

  The effect of DMSO on the borohydride reduction of a cyclohexanone: A formal enantioselective synthesis of (+)-epibatidine

  摘要：

  An asymmetric synthesis of (+)-epibatidine is described which uses the increased stereoselectivity of a borohydride reduction induced by the presence of DMSO. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02354-5

文献信息

• Approaches to the synthesis of (+)- and (−)-epibatidine †
  作者：M. Teresa Barros、Christopher D. Maycock、M. Rita Ventura

  DOI：10.1039/b002980g

  日期：——

  Synthetic approaches to the powerful analgesic alkaloids (+)- and (−)-epibatidine are described. The starting material employed was natural (−)-quinic acid from which chiral enones and α-iodoenones were prepared. Stille coupling afforded suitable substrates for completion of the syntheses. A key step in this process was the diastereoselective reduction of a cyclohexanone with sodium borohydride and DMSO which sets up the stereochemistry necessary for the formation of the bicycloheptane system. The synthesis of a previously reported enone intermediate has also been improved. p

  本文介绍了强效镇痛生物碱(+)-和(â)-表巴丁的合成方法。采用的起始原料是天然(â)-奎宁酸，并从中制备了手性烯酮和δ-碘烯酮。斯蒂尔偶联为完成合成提供了合适的底物。这一过程中的一个关键步骤是用硼氢化钠和二甲基亚砜对环己酮进行非对映选择性还原，从而建立了形成双环庚烷体系所需的立体化学结构。之前报道的一种烯酮中间体的合成方法也得到了改进。
• Total Synthesis and Structural Reassignment of (+)-Dictyosphaeric Acid A: A Tandem Intramolecular Michael Addition/Alkene Migration Approach
  作者：Alan R. Burns、Graeme D. McAllister、Stephen E. Shanahan、Richard J. K. Taylor

  DOI：10.1002/anie.201002416

  日期：——

  The acid test? The synthetic route to the title compound features a Z‐selective ring‐closing metathesis reaction and an E‐selective tandem intramolecular Michael addition/alkene migration sequence as the key transformations. The stereochemical configuration of the product was reassigned based on NMR studies.

  酸测试？标题化合物的合成途径具有Z选择性闭环易位反应和E选择性串联分子内迈克尔加成/烯烃迁移序列作为关键转化。根据NMR研究，重新分配了产品的立体化学构型。
• A Convergent Synthesis of the Tricyclic Core of the Dictyosphaeric Acids
  作者：Christopher W. Barfoot、Alan R. Burns、Michael G. Edwards、Martin N. Kenworthy、Mahmood Ahmed、Stephen E. Shanahan、Richard J. K. Taylor

  DOI：10.1021/ol702887e

  日期：2008.1.1

  The first synthetic route to the tricyclic core of the dictyosphaeric acids has been established starting from readily available (S)-(-)-4-(tert-butyldimethylsilyloxy)cyclohexenone and involving 9 steps, including a ring-closing metathesis to produce a 13-membered macrolactone, and a doubly tethered intramolecular Michael addition.