3-(trimethylsilyl)-2-propynyl triphenyl arsonium bromide | 117953-07-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-(trimethylsilyl)-2-propynyl triphenyl arsonium bromide
• 英文别名: Triphenyl(3-trimethylsilylprop-2-ynyl)arsanium;bromide
• CAS: 117953-07-8
• 化学式: Br*C₂₄H₂₆AsSi
• 分子量: 497.382
• InChiKey: DFWNSKKDYDSUGN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.04
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(trimethylsilyl)-2-propynyl triphenyl arsonium bromide 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.53h， 生成 (E)-1-pyrrolidin-1-yl-5-trimethylsilylpent-2-en-4-yn-1-one
  参考文献：
  名称：

  A Novel One-Pot Synthesis of 2,4-Enynyl Amides

  摘要：

  Silylated 2,4-enynyl amides can be synthesized by the reaction of 3-(trimethylsilyl)-2-propynylidenetriphenylarsorane, generated in situ from the corresponding arsonium salt and n-butyllithium, with alpha-bromoacetamides in 40-59% yields (two steps) and with high stereoselectivity.

  DOI：

  10.1080/00397919108019804
• 作为产物：
  描述：

  三苯胂 、 3-溴-1-三甲基硅基-1-丙炔 以 乙腈 为溶剂， 反应 48.0h， 以97%的产率得到3-(trimethylsilyl)-2-propynyl triphenyl arsonium bromide
  参考文献：
  名称：

  通过甲硅烷基化的son鎓内鎓盐合成末端三甲基甲硅烷基烯炔

  摘要：

  由相应的砷盐和正丁基锂在原位生成的3-（三甲基甲硅烷基）-2-丙炔基内苯三甲ar烷与酮的反应以72-100％的收率得到末端三甲基甲硅烷基烯炔。立体化学研究表明，底物的结构表现出深远的影响，特别是当大的叔丁基与羰基相邻时。在这种情况下，E-异构体仅形成。相应的膦烷不与叔丁基甲基酮反应，而与其他酮反应，产率要低得多。

  DOI：

  10.1016/0022-328x(88)80114-1

文献信息

• A Facile Synthesis of (Trimethylsilylethynyl)cyclopropanes via an Arsonium Ylide
  作者：Yanchang Shen、Qimu Liao

  DOI：10.1055/s-1988-27556

  日期：——

  The reaction of 3-(trimethylsilyl)-2-propynylidenetriphenylarsorane, generated in situ from the corresponding arsonium salt and butyllithium, with chalcones (as α,β-unsaturated ketones) gives (trimethylsilylethynyl)cyclopropanes in 96-100% yield and with high stereoselectivity.

  3-(三甲基硅基)-2-丙炔亚烯（三苯基砷烷）与查尔酮（作为α,β-不饱和酮）的反应，采用原位生成的相应砷盐和丁基锂，能够以96-100%的产率和高立体选择性生成（三甲基硅基炔基）环丙烷。
• Synthesis of (trimethylsilyl)(cyclopropyl)acetylenes and terminal cyclopropylacetylenes via an arsonium ylide under phase-transfer conditions
  作者：Yanchang Shen、Qimu Liao

  DOI：10.1016/0022-328x(89)85204-0

  日期：1989.7

  The phase-transfer reaction of 3-(trimethylsilyl)-2-propynylidenetriphenylarsorane generated from the corresponding arsonium salt and aqueous sodium hydroxide with substituted chalcones gave (trimethylsilyl)(cyclopropyl)acetylenes in 83–98% yields with high stereoselectivity. In all cases exclusively one isomer is obtained. Addition of methanol gives the desilylated terminal cyclopropylacetylenes in

  由相应的son盐和氢氧化钠水溶液与取代的查耳酮生成的3-（三甲基甲硅烷基）-2-丙炔基内苯三甲ar烷进行相转移反应，制得的（三甲基甲硅烷基）（环丙基）乙炔的立体选择性高，为83-98％。在所有情况下，仅获得一种异构体。加入甲醇可得到脱甲硅烷基化的末端环丙基乙炔，产率为85–96％。该方法学提供了到达（三甲基甲硅烷基）（环丙基）乙炔并随后去甲硅烷基化的末端环丙基乙炔的便利途径。
• 3-Hydroxyleukotriene B4 (3-OH-LTB4): Total Synthesis and Stereochemical Assignment.
  作者：Rama K. Bhatt、Kamlesh Chauhan、Pat Wheelan、J. R. Falck、Robert C. Murphy

  DOI：10.1021/ja00091a004

  日期：1994.6

  The asymmetric total synthesis of 3-hydroxyleukotriene B-4 (3-OH-LTB(4)), an ethanol-inducible proinflammatory autacoid, was achieved using a triply convergent strategy for the sequential union of propargylic arsonium salt 3 with pyranosides 2a,b and furanose 4. Both saccharide subunits were derived from commercial 2-deoxy-D-ribose. The key transformation involved palladium-mediated coupling of bromoacetylenide 9 with stannylglycal 6a,b. Subsequent Rieke zinc hydrogenation of acetylene 10a,b and controlled ionic reduction of the cross-conjugated cyclic enol ether using NaBH3CN at pH similar to 4-4.5 established the cis-Delta(6,7)-olefin and C(5)-hydroxyl stereochemistry, respectively, and led to 11a,b. Methyllactol hydrolysis, PCC oxidation, methanolysis, and desilylation afforded 3(R)- and 3(S)-OH-LTB(4) methyl esters, respectively. On the basis of chromatographic and mass spectral comparisons, enzymatically derived 3-OH-LTB(4) is composed principally of the 3(S)-isomer (>95%).
• A Novel One-Pot Synthesis of 2,4-Enynyl Amides
  作者：Yanchang Shen、Yuejun Xiang

  DOI：10.1080/00397919108019804

  日期：1991.10

  Silylated 2,4-enynyl amides can be synthesized by the reaction of 3-(trimethylsilyl)-2-propynylidenetriphenylarsorane, generated in situ from the corresponding arsonium salt and n-butyllithium, with alpha-bromoacetamides in 40-59% yields (two steps) and with high stereoselectivity.
• Synthesis of terminal trimethylsilyl enynes via a silylated arsonium ylide
  作者：Yanchang Shen、Qium Liao

  DOI：10.1016/0022-328x(88)80114-1

  日期：1988.5

  The reaction of 3-(trimethylsilyl)-2-propynylidenetriphenylarsorane, generated in situ from the corresponding arsonium salt and n-butyllithium, with ketones gave terminal trimethylsilyl enynes in 72–100% yields. The stereochemical study revealed that the structure of the substrate displayed a profound effect, especially when a bulky t-butyl group was adjacent to the carbonyl group; in this case the

  由相应的砷盐和正丁基锂在原位生成的3-（三甲基甲硅烷基）-2-丙炔基内苯三甲ar烷与酮的反应以72-100％的收率得到末端三甲基甲硅烷基烯炔。立体化学研究表明，底物的结构表现出深远的影响，特别是当大的叔丁基与羰基相邻时。在这种情况下，E-异构体仅形成。相应的膦烷不与叔丁基甲基酮反应，而与其他酮反应，产率要低得多。