(trimethylacetyl)(phenyl{[(trifluoromethyl)sulfonyl]oxy}iodo)acetylene | 134938-34-4

• 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: (trimethylacetyl)(phenyl{[(trifluoromethyl)sulfonyl]oxy}iodo)acetylene
• 英文别名: (4,4-Dimethyl-3-oxopent-1-ynyl)-phenyliodanium;trifluoromethanesulfonate
• CAS: 134938-34-4
• 化学式: CF₃O₃S*C₁₃H₁₄IO
• 分子量: 462.228
• InChiKey: CJDAWNSWEHPBEW-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -0.43
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  82.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (trimethylacetyl)(phenyl{[(trifluoromethyl)sulfonyl]oxy}iodo)acetylene 在 rhodium(II) acetate dimer 、 sodium amalgam 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 17.5h， 生成 spiro[8-hydroxy-1,4,4,8-tetramethyl-10-oxatricyclo[5.2.1.0^2,6]deca-3,8-dione-9,1'-cyclopropane]
  参考文献：
  名称：

  An Approach toward the Illudin Family of Sesquiterpenes Using the Tandem Cyclization−Cycloaddition Reaction of Rhodium Carbenoids

  摘要：

  The Rh(II)-catalyzed reaction of 1-acetyl-1-(diazoacetyl)cyclopropane with 5,5-dimethylcyclopentenone afforded the product of a 1,3-dipolar cycloaddition in high yield. The reaction involves formation of a rhodium carbenoid and subsequent transannular cyclization of the electrophilic carbon onto the adjacent keto group to generate a five-membered cyclic carbonyl ylide which undergoes a subsequent 1,3-dipolar cycloaddition reaction. The regiochemical results encountered can be rationalized on the basis of FMO considerations. Treatment of the cycloadduct with p-toluene-sulfonic acid results in loss of water followed by a subsequent acid-catalyzed cyclopropyl ketone rearrangement to give dihydrobenzofuran 21. The product distribution derived from the SmI2-induced reduction of the dipolar cycloadduct was found to depend on the reaction conditions. Under kinetic conditions, the reduction resulted in opening of the cyclopropyl ring adjacent to the carbonyl group. However, under thermodynamic conditions, cleavage of the oxy bridge corresponded to the major pathway. The cycloaddition-reduction protocol provides a rapid assembly of the basic core unit of ptaquilosin having most of the functionality in place. Generation of a carbanion adjacent to the oxy bridge leads to opening of the oxabicyclic ring system in a highly regioselective manner. A short synthesis of (+/-)-illudin M and the closely related isodehydroilludin M is described in which the key step involves a dipolar cycloaddition using a carbonyl ylide.

  DOI：

  10.1021/jo961574i
• 作为产物：
  描述：

  oxy>iodo>benzene 、 (trimethylacetyl)(triethylstannyl)acetylene 以 二氯甲烷 为溶剂， 以82%的产率得到(trimethylacetyl)(phenyl{[(trifluoromethyl)sulfonyl]oxy}iodo)acetylene
  参考文献：
  名称：

  Preparation of functionalized alkynyl(phenyl)iodonium salts via a novel iodonium transfer process between alkynylstannanes and PhI+CN -OTf

  摘要：

  DOI：

  10.1021/ja00015a055

文献信息

• [3+2]-Cycloaddition reactions of alkynyl(phenyl)iodonium triflates with ethyl diazoacetate, N-t-butyl-α-phenyl nitrone and t-butylnitrileoxide as 1,3-dipoles
  作者：Peter J. Stang、Paul Murch

  DOI：10.1016/s0040-4039(97)10418-x

  日期：1997.12

  The [3+2]-cycloaddition of various β-substituted ethynyliodonium salts, RCCl+O−Tf, with ethyl diazoacetate, N-t-butyl-α-phenyl nitrone and t-butylnitrile oxide results in single regioisomeric pyrroles, dihydroisoxazoles, and isoxazoles respectively in moderate yields.

  各种β-取代的乙炔碘铵盐RCCl + O - Tf与重氮乙酸乙酯，Nt-丁基-α-苯基硝酮和叔丁基腈的[3 + 2]-环加成反应会生成单一的区域异构吡咯，二氢异恶唑分别以中等收率生产异恶唑。
• 1,3-Dipolar cycloaddition reactions of α-diazocarbonyl compounds, organoazides, and ethynyl(phenyl)iodonium triflate salts
  作者：Gerhard Maas、Manfred Regitz、Ulrich Moll、Rainer Rahm、Fred Krebs、Rudolf Hector、Peter J. Stang、Charles M. Crittell、Bobby L. Williamson

  DOI：10.1016/s0040-4020(01)88491-x

  日期：1992.1

  RCCI+ -Ph·TfO- (1, R = H, SiMe3, tBuCO) undergoes [2+3] cycloaddition with α-diazocarbonyl compounds. Whereas 1:1 cycloadducts (4a–d,6) are obtained for R = SiMe3 or tBuCO (X-ray structure analysis of 4b), diazoacetic esters react with two equivalents of the parent alkyne (1, R = H) to form bis-iodonium salts 9. Cycloaddition of methyl or phenyl azide to 1 yields (1,2,3-triazoly-4-yl)iodonium salts (13

  RCCI的贫电子三键+ -Ph·TFO - （1，R = H，森达3，吨BUCO）经历[2 + 3]环加成用α-diazocarbonyl化合物。对于R = SiMe 3或tBuCO（4b的X射线结构分析），可获得1：1的加合物（4a–d，6），重氮乙酸酯与两当量的母体炔烃（1，R = H）反应形成双碘盐9。甲基或苯基叠氮化物的环加成1个产率（1,2,3- triazoly -4-基）碘鎓盐（13,14）的低收率。
• Ready Formation of Functionalized Alkynyl Phenyl Selenides and Tellurides Via Alkynyliodonium Triflates
  作者：Peter J. Stang、Paul Murch

  DOI：10.1055/s-1997-1386

  日期：1997.12

  Reactions of β-functionalized alkynyliodonium triflates with PhSeK or PhTeLi afford novel, push-pull alkynyl phenyl selenides and tellurides in good yields.

  β-功能化的炔基碘鎓三氟甲磺酸盐与 PhSeK 或 PhTeLi 反应，生成新型的推拉型炔基苯基硒化物和碲化物，产率良好。
• Push-Pull Ynamines via Alkynyliodonium Chemistry
  作者：Paul Murch、Bobby L. Williamson、Peter J. Stang

  DOI：10.1055/s-1994-25675

  日期：——

  The reaction of substituted alkynyl(phenyl)iodonium salts 3a-e with lithium diphenylamine (LiNPh2) leading to the formation of push-pull ynamine products 5a-e is described.

  描述了取代的炔基(苯基)碘鎓盐3a-e与二苯胺锂(LiNPh2)反应生成推拉型ynamine产物5a-e的过程。
• Williamson, Bobby L.; Stang, Peter J.; Arif, Atta M., Journal of the American Chemical Society, 1993, vol. 115, # 7, p. 2590 - 2595
  作者：Williamson, Bobby L.、Stang, Peter J.、Arif, Atta M.

  DOI：——

  日期：——