E-trichloro-(3-phenyl-allyl)-silane

• 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: E-trichloro-(3-phenyl-allyl)-silane
• 英文别名: trichloro-[(E)-3-phenylprop-2-enyl]silane
• 化学式: C₉H₉Cl₃Si
• 分子量: 251.615
• InChiKey: MKNDNHJXOZTTSU-QPJJXVBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1S,2S)-2-甲氨基-1-苯基丙-1-醇 、 E-trichloro-(3-phenyl-allyl)-silane 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以83%的产率得到(4S,5S)-2-chloro-3,4-dimethyl-5-phenyl-2-[(E)-3-phenylprop-2-enyl]-1,3,2-oxazasilolidine
  参考文献：
  名称：

  Highly Enantioselective Imine Cinnamylation with a Remarkable Diastereochemical Switch

  摘要：

  The first general method for the enantioselective cinnamylation of aldimines is reported. The method utilizes a simple chiral cinnamylsilane reagent and is characterized by experimental simplicity and extraordinarily high levels of enantioselectivity. Further, a remarkable and unprecedented diastereochemical reversal has been realized whereby either diastereomer may be accessed from the same trans-cinnamylsilane based upon a subtle change to the imine, thus obviating the usual requirement for both the trans- and cis-cinnamylsilanes.

  DOI：

  10.1021/ja076035h
• 作为产物：
  描述：

  肉桂基氯 在 三氯硅烷 、 N,N-二异丙基乙胺 、 copper(l) chloride 作用下， 以 乙醚 为溶剂， 生成 E-trichloro-(3-phenyl-allyl)-silane
  参考文献：
  名称：

  由烯丙基卤化物一锅对映选择性合成旋光均烯醇。

  摘要：

  开发了一种一锅方便的方法，用于从烯丙基卤化物制备光学活性均烯丙基醇。在氯化亚铜和叔胺存在下，由烯丙基卤和三氯硅烷原位生成烯丙基三氯硅烷。在不分离烯丙基三氯硅烷的情况下，将苯甲醛和手性联喹啉N，N′-二氧化物引入同一烧瓶中，产生具有良好至高对映选择性的相应的均烯丙基醇。

  DOI：

  10.1248/cpb.48.306

文献信息

• Structure influence of chiral 1,1′-biscarboline-N,N′-dioxide on the enantioselective allylation of aldehydes with allyltrichlorosilanes
  作者：Bing Bai、Hua-Jie Zhu、Wei Pan

  DOI：10.1016/j.tet.2012.06.042

  日期：2012.8

  A series of new axially chiral 1,1′-biscarboline-N,N′-dioxide Lewis base organocatalysts were examined in the asymmetric allylation of aldehydes with allyltrichlorosilane. The chiral catalysts (R)-1a–e bearing ester groups in 3,3′ position provided good yields of the homoallyl alcohols with excellent enantioselectivities up to 99% for a broad substrate scope that covers aliphatic, aromatic, heteroaromatic

  在醛与烯丙基三氯硅烷的不对称烯丙基化反应中，研究了一系列新型的轴向手性1,1'-双咔啉-N，N'-二氧化物路易斯碱有机催化剂。的手性催化剂（[R ）- 1A - ë轴承酯基团在3,3'位置上设置具有优异的对映选择性高达99％的高烯丙基醇的良好的产率为广泛的底物范围，其覆盖脂族，芳香族，杂芳香族，和α，β -不饱和醛。阐明了溶剂对转化率和对映选择性的影响，并确定了CH 2 Cl 2被证明是反应的最佳溶剂。另外，还探索了与巴豆基三氯硅烷的烯丙基化反应，结果表明，（E）-巴豆基三氯硅烷具有较好的非对映选择性，有利于其抗异构体的形成。
• Chiral sulfoxides as activators of allyl trichlorosilanes in the stereoselective allylation of aldehydes
  作者：Vincenzo De Sio、Antonio Massa、Arrigo Scettri

  DOI：10.1039/c002988b

  日期：——

  Chiral aryl methyl sulfoxides proved to be efficient activators in the asymmetric allylation of aldehydes with allyl trichlorosilanes. High enantioselectivity was found in the case of electron-poor aldehydes. The high levels of diastereoselectivity and the detection of nonlinear effects have allowed the elucidation of some mechanistic aspects of the reaction.

  手性芳基甲基亚砜在不对称烯丙基化醛与烯丙基三氯硅烷反应中被证明是有效的催化剂。对于电子贫穷的醛，发现了高的对映选择性。高水平的差向选择性及非线性效应的检测使得反应的一些机理方面得以阐明。
• One-pot Enantioselective Synthesis of Optically Active Homoallylic Alcohols from Allyl Halides.
  作者：Makoto KANAJIMA、Makoto SAITO、Shunichi HASHIMOTO

  DOI：10.1248/cpb.48.306

  日期：——

  active homoallylic alcohols from allyl halides was developed. Allyltrichlorosilanes were generated in situ from allyl halides and trichlorosilane in the presence of cuprous chloride and tertiary amine. Without isolation of the allyltrichlorosilanes, benzaldehyde and chiral biquinoline N,N'-dioxide were introduced into the same flask, producing the corresponding homoallylic alcohols with good to high

  开发了一种一锅方便的方法，用于从烯丙基卤化物制备光学活性均烯丙基醇。在氯化亚铜和叔胺存在下，由烯丙基卤和三氯硅烷原位生成烯丙基三氯硅烷。在不分离烯丙基三氯硅烷的情况下，将苯甲醛和手性联喹啉N，N′-二氧化物引入同一烧瓶中，产生具有良好至高对映选择性的相应的均烯丙基醇。
• Diastereoselective Addition of Prochiral Nucleophilic Alkenes to α-Chiral <i>N</i>-Sulfonyl Imines
  作者：David A. Gutierrez、James Fettinger、K. N. Houk、Kaori Ando、Jared T. Shaw

  DOI：10.1021/acs.orglett.1c04219

  日期：2022.2.11

  to chiral α-alkoxy N-tosyl imines is described. Alkene geometry is selectively transferred to the newly formed carbon–carbon bond, resulting in stereochemical control of C1, C2, and C3 of the resulting 2-alkoxy-3-N-tosyl-4-alkyl-5-hexene products. A computational analysis to elucidate the high selectivity is also presented. This methodology was employed in the synthesis of two naturally occurring isomers

  描述了路易斯酸促进前手性E-和Z-烯丙基亲核试剂与手性 α-烷氧基N-甲苯磺酰基亚胺的加成。烯烃几何结构选择性地转移到新形成的碳-碳键上，从而对所得 2-烷氧基-3- N-甲苯磺酰基-4-烷基-5-己烯产物的 C1、C2 和 C3 进行立体化学控制。还提出了阐明高选择性的计算分析。该方法用于合成两种天然存在的硫磺酰胺异构体。
• Highly Enantioselective Imine Cinnamylation with a Remarkable Diastereochemical Switch
  作者：John D. Huber、James L. Leighton

  DOI：10.1021/ja076035h

  日期：2007.11.28

  The first general method for the enantioselective cinnamylation of aldimines is reported. The method utilizes a simple chiral cinnamylsilane reagent and is characterized by experimental simplicity and extraordinarily high levels of enantioselectivity. Further, a remarkable and unprecedented diastereochemical reversal has been realized whereby either diastereomer may be accessed from the same trans-cinnamylsilane based upon a subtle change to the imine, thus obviating the usual requirement for both the trans- and cis-cinnamylsilanes.