tert-butyldiphenyl[(5-phenylpent-4-yn-1-yl)oxy]silane

• 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
• 英文名称: tert-butyldiphenyl[(5-phenylpent-4-yn-1-yl)oxy]silane
• 英文别名: 1-tert-butyldiphenylsilyloxy-5-phenyl-4-pentyne；Tert-butyl-diphenyl-(5-phenylpent-4-ynoxy)silane；tert-butyl-diphenyl-(5-phenylpent-4-ynoxy)silane
• 化学式: C₂₇H₃₀OSi
• 分子量: 398.62
• InChiKey: POGXKPKKGFGUQE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyldiphenyl[(5-phenylpent-4-yn-1-yl)oxy]silane 在 η1,η5-(5,5-dimethyldipyrrolylmethane)bis(dimethylamido)titanium(IV) 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 50.0h， 生成 6-{3-[(tert-butyldiphenylsilyl)oxy]propyl}-5-phenyl-2-(phenylamino)nicotinonitrile
  参考文献：
  名称：

  Titanium-Catalyzed, One-Pot Synthesis of 2-Amino-3-cyano- pyridines

  摘要：

  AbstractEarth‐abundant and inexpensive titanium can catalyze alkyne iminoamination, which generates tautomers of 1,3‐diimines. Upon treatment with base (DBU) and malononitrile, the multicomponent coupling product is converted to 2‐amino‐3‐cyanopyridines in a one‐pot procedure in good to modest yields. There is substantial control of regioselectivity for the substituents on the pyridine ring and on the 2‐amino group. Several studies were done that provide significant evidence for a Dimroth rearrangement mechanism for 2‐aminopyridine formation, including isolation of a 2‐imino‐1,2‐dihydropyridine intermediate that undergoes rearrangement under the reaction conditions.magnified image

  DOI：

  10.1002/adsc.201301046
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 乙二胺 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 以95%的产率得到tert-butyldiphenyl[(5-phenylpent-4-yn-1-yl)oxy]silane
  参考文献：
  名称：

  Novel decomplexation method for alkyne–Co2(CO)6 complexes

  摘要：

  A novel and general decomplexation method for alkyne-Co-2(CO)(6) complexes has been established, which treats the complexes with ethylenediamine in THF. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(97)00679-7

文献信息

• Stereoselective Synthesis of Tetrasubstituted Alkenes via a Cp*Co ^III ‐Catalyzed C−H Alkenylation/Directing Group Migration Sequence
  作者：Hideya Ikemoto、Ryo Tanaka、Ken Sakata、Motomu Kanai、Tatsuhiko Yoshino、Shigeki Matsunaga

  DOI：10.1002/anie.201703193

  日期：2017.6.12

  economical and stereoselective synthesis of tetrasubstituted α,β‐unsaturated amides was achieved by a Cp*CoIII‐catalyzed C−H alkenylation/directing group migration sequence. A carbamoyl directing group, which is typically removed after C−H functionalization, worked as an internal acylating agent and migrated onto the alkene moiety of the product. The directing group migration was realized with the

  通过Cp * Co III催化的CH烯基化/方向基团迁移序列，实现了高度原子经济和立体选择性的四取代α，β-不饱和酰胺的合成。通常在CH官能化后被除去的氨基甲酰基导向基团作为内部酰化剂起作用，并迁移到产物的烯烃部分上。使用Cp * Co III催化剂可实现导向基团的迁移，而相关的Cp * Rh III催化剂则不会促进迁移过程。将产物进一步转化为两种类型的三环化合物，其中一种具有荧光性质。
• Pyrroloindolone Synthesis via a Cp*Co^III-Catalyzed Redox-Neutral Directed C–H Alkenylation/Annulation Sequence
  作者：Hideya Ikemoto、Tatsuhiko Yoshino、Ken Sakata、Shigeki Matsunaga、Motomu Kanai

  DOI：10.1021/ja5008432

  日期：2014.4.9

  A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was

  描述了 Cp*Co(III) 催化剂与相关 Cp*Rh(III) 催化剂相比的独特合成效用。C2 选择性吲哚烯基化/环化序列在催化量的 [Cp*Co(III)(C6H6)](PF6)2 复合物和 KOAc 的作用下顺利进行。将烯基-Cp*Co 物质分子内加成到氨基甲酰基部分，在一锅中以 58-89% 的产率得到吡咯并吲哚酮。在 Cp*Co(III) 配合物和 Cp*Rh(III) 配合物的催化活性之间观察到明显的差异，突出了有机钴物种独特的亲核活性。Cp*Co(III) 催化也适用于 N-氨基甲酰基吲哚的简单烯基化过程，广泛的炔烃，包括末端炔烃，适用于以 50-99% 的产率得到 C2-烯基化吲哚。
• Scandium-Catalyzed Regio- and Stereospecific Methylalumination of Silyloxy/Alkoxy-Substituted Alkynes and Alkenes
  作者：Masanori Takimoto、Saori Usami、Zhaomin Hou

  DOI：10.1021/ja909126k

  日期：2009.12.30

  Various alkynes and alkenes having a tethered ether group undergo methylalumination reactions with unprecedented regio- and stereoselectivity in the presence of a cationic half-sandwich alkylscandium species as a catalyst. The oxygen atom of the ether group plays an important role in controlling the selectivity, possibly by coordinating to the metal center. Even when a bulky tertbutyl(diphenyl)silyloxy group is used as the tether group, there is no loss of selectivity.
• Novel decomplexation method for alkyne–Co2(CO)6 complexes
  作者：Takumichi Sugihara、Hitoshi Ban、Masahiko Yamaguchi

  DOI：10.1016/s0022-328x(97)00679-7

  日期：1998.3

  A novel and general decomplexation method for alkyne-Co-2(CO)(6) complexes has been established, which treats the complexes with ethylenediamine in THF. (C) 1998 Elsevier Science S.A. All rights reserved.
• Titanium-Catalyzed, One-Pot Synthesis of 2-Amino-3-cyano- pyridines
  作者：Amila A. Dissanayake、Richard J. Staples、Aaron L. Odom

  DOI：10.1002/adsc.201301046

  日期：2014.5.26

  AbstractEarth‐abundant and inexpensive titanium can catalyze alkyne iminoamination, which generates tautomers of 1,3‐diimines. Upon treatment with base (DBU) and malononitrile, the multicomponent coupling product is converted to 2‐amino‐3‐cyanopyridines in a one‐pot procedure in good to modest yields. There is substantial control of regioselectivity for the substituents on the pyridine ring and on the 2‐amino group. Several studies were done that provide significant evidence for a Dimroth rearrangement mechanism for 2‐aminopyridine formation, including isolation of a 2‐imino‐1,2‐dihydropyridine intermediate that undergoes rearrangement under the reaction conditions.magnified image