| 451485-86-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• CAS: 451485-86-2
• 化学式: C₆H₁₀BrClSiZn
• 分子量: 290.978
• InChiKey: YZQFLCQCUTXSPM-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.49
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (E)-2-methyl-N-(2-methylpropylidene)propane-2-sulfinamide 、 在 六甲基磷酰三胺 作用下， 以 乙醚 、 正己烷 为溶剂， 生成 (R_S,2R,3R)-(-)-N-(tert-butanesulfinyl)-3-isopropyl-2-[(trimethylsilyl)ethynyl]aziridine
  参考文献：
  名称：

  三（二甲基苯基甲硅烷基）锌酸锂对N-叔丁烷亚磺酰基乙炔基氮丙啶的开环反应：立体选择性地获得4-氨基-1-烯丙基硅烷

  摘要：

  据报道，N-叔丁烷亚磺酰基乙炔基氮丙啶与三（二甲基苯基甲硅烷基）锌酸锂开环。该反应被证明既具有立体选择性也具有立体特异性，并且会通过抗-S N 2'过程进行。在温和条件下对氮原子进行进一步的脱保护，可以以高收率和立体选择性的水平获得4-氨基-1-（二甲基苯基甲硅烷基）丙烯。

  DOI：

  10.1002/adsc.201500347
• 作为产物：
  描述：

  (3-chloro-1-propynyl)trimethylsilane 、 zinc dibromide 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  烯丙基锌试剂：新趋势和合成应用

  摘要：

  总结了我们在研究中涉及到的烯丙基锌试剂的最新进展。这些有趣有机金属化合物 允许乙炔的立体选择性和对映选择性合成 环氧化物，氮丙啶和氨基醇。这些高功能化底物的一些合成应用也通过合成均丙醇和烯丙二酸而得到了展示。酮类。还讨论了在杂环天然产物的全合成中的进一步应用。

  DOI：

  10.1039/b706541h

文献信息

• Allenylzincs and tert-butylsulfinylimines: a fruitful marriage for synthesis
  作者：Candice Botuha、Fabrice Chemla、Franck Ferreira、Julien Louvel、Alejandro Pérez-Luna

  DOI：10.1016/j.tetasy.2010.04.044

  日期：2010.5

  2-amino alcohols by the addition of 3-chloro- and 3-methoxymethoxy- allenylzincs to chiral tert-butylsulfinylimines is described. The methodology is applicable to the preparation of alkynyl 2-amino-1,3-diols (O,N,O stereotriads) using α-alkoxy tert-butylsulfinylimines as chiral starting materials. The scope and limitations of the methodology along with recent applications to the efficient asymmetric syntheses

  描述了通过将3-氯-和3-甲氧基甲氧基-烯丙基锌锌添加到手性叔丁基亚磺酰亚胺中的炔基1,2-氨基醇的立体选择性合成。该方法适用于使用α-烷氧基叔丁基亚磺酰亚胺的手性原料制备炔基2-氨基-1,3-二醇（O，N，O立体三单元）。介绍了该方法的范围和局限性，以及对天然和/或生物活性生物碱和多羟基化生物碱的有效不对称合成的最新应用。
• High Kinetic Resolution in the Addition of a Racemic Allenylzinc onto Enantiopure <i>N</i>-<i>tert</i>-Butanesulfinimines:  Concise Synthesis of Enantiopure <i>trans</i>-2-Ethynylaziridines¹
  作者：Fabrice Chemla、Franck Ferreira

  DOI：10.1021/jo0490696

  日期：2004.11.1

  Enantiopure trans-ethynyl N-tert-butanesulfinylaziridines (R-s)-6 were prepared in good to excellent yields by the condensation of the racemic allenylzinc species 1 derived from 3-chloro-l-trimethyl-silylpropyne onto the corresponding enantiopure N-tert-butanesulfinimines (R-s)-5. The absolute stereochemistry of enantiopure N-tert-butanesulfinylaziridines (R-s)-6 was shown to be (R-s,2R,3R) and results from a chelate-type transition state in which the zinc atom of allenylzinc 1 is coordinated by both the nitogen and the oxygen atoms of the imine. Further removal of the N-tert-butanesulfinyl auxiliary of alkyl 3-substituted and 3,3-disubstituted ethynyl N-tert-butanesulfinylaziridines (Rs)-6 could be achieved by treatment with HCl in MeOH affording the corresponding deprotected aziridines (2R,3R)-9 and (2R)-9 respectively as enantiomerically pure compounds.
• An Efficient Synthesis of Epoxydiynes and a Key Fragment of Neocarzinostatin Chromophore
  作者：J. R. Baker、O. Thominet、H. Britton、S. Caddick

  DOI：10.1021/ol062461g

  日期：2007.1.1

  A key structural feature of the Neocarzinostatin chromophore is a reactive epoxydiyne. We present here a new method for the preparation of epoxydiynes by the addition of an allenyl zinc bromide to a propargylic ketone.
• Double Deprotonation of Acetylenic Oxiranes:  Synthesis of Allenic Ketones through Dilithio Ynenolates
  作者：Aurélien Denichoux、Franck Ferreira、Fabrice Chemla

  DOI：10.1021/ol048630j

  日期：2004.9.1

  The double deprotonation of acetylenic oxiranes gives allenic ketones through the 1,2-H or 1,2-Ar shift on the transient oxiranyl dianion intermediates. The resulting dilithium ynenolates give allenic ketones upon hydrolysis or can be quenched with various electrophiles.
• Metallotropic Equilibrium and Configurational Stability of 3-Chloro-1-(trimethylsilyl)propargyl and -allenyl Metals: Comparative Study among Lithium, Titanium, and Zinc
  作者：Joseph Bejjani、Candice Botuha、Fabrice Chemla、Franck Ferreira、Sarah Magnus、Alejandro Pérez-Luna

  DOI：10.1021/om300420q

  日期：2012.7.9

  A comparative study of the metallotropic equilibrium between 1-chloro-3-(trimethylsilyl)propargyl and -allenyl metals was undertaken by means of lithio-, titano-, and zinco-carbenoids. The lithium and zinc species were shown to react mainly in their allenic metallotropic forms, whereas the titanium species proved to react in both its propargylic and allenic forms. The configurational stability of these organometallics was next examined using a modification of the Hoffmann test. In each case, the organometallic was reacted with a chiral enantiopure electrophile. A comparison of the diastereomeric ratios obtained at low and high conversion rates of the reagent allows assessment of its configurational stability. The lithium species thus exhibited a configurational lability at -125 degrees C in Trapp mixture on the time scale of its reaction with (+)-camphor, while the titanium analogue proved to be configurationally stable at -40 degrees C in THF/Et2O on the time scale defined by its reaction with (S)-N-tritylprolinal. In the context of its reaction with the same electrophile, the zinc bromide species was proven to be partially labile from -80 degrees C in THF and its dynamic kinetic resolution was investigated.