1-(2,2-dimethylpropyl)-2-trimethylsilyl-1H-1,3-benzazaphosphole | 1039451-42-7

• 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: 1-(2,2-dimethylpropyl)-2-trimethylsilyl-1H-1,3-benzazaphosphole
• 英文别名: [1-(2,2-Dimethylpropyl)-1,3-benzazaphosphol-2-yl]-trimethylsilane；[1-(2,2-dimethylpropyl)-1,3-benzazaphosphol-2-yl]-trimethylsilane
• CAS: 1039451-42-7
• 化学式: C₁₅H₂₄NPSi
• 分子量: 277.422
• InChiKey: RQXMXPHDAFIARR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.81
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  4.9
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  三甲基氯硅烷 、 生成 1-(2,2-dimethylpropyl)-2-trimethylsilyl-1H-1,3-benzazaphosphole
  参考文献：
  名称：

  Ambident Reactivity of P˭CH‒N‒Heterocycles: Lithiation and Substitution Sites

  摘要：

  Benzofused 1H-1,3-azaphospholes are lithiated at the N-atom by tBuLi but phosphinylation takes place at either the N- or the P-atom. Smaller chlorophosphines react at nitrogen, bulkier react at phosphorus. Substituents at C2 promote the latter mode. N- Substituted 2H-1,3-benzazaphospholes undergo CH-metalation or addition at the P=C bond, depending on the conditions, and allow access to 2-functionally substituted benzazaphospholes or their 2,3-dihydro derivatives, new sigma P-2,X or sigma P-3,X hybrid ligands (X=O,P).

  DOI：

  10.1080/10426507.2010.514486

文献信息

• Sterically and Polarity-Controlled Reactions oftBuLi with PCH-NR Heterocycles: Novel Heterocyclic P- and P,O-Ligands and Preliminary Tests in Transition-Metal Catalysis
  作者：Bhaskar R. Aluri、Markus K. Kindermann、Peter G. Jones、Joachim Heinicke

  DOI：10.1002/chem.200702016

  日期：2008.5.9

  reactivity towards addition at the P=C bond. The preferred regioselectivity is tert-butylation at phosphorus, occurring with excellent diastereoselectivity for trans-adducts 3 b and 3 c, but the inverse tert-butylation at C2 to 5 b was also observed. N-Neopentyl groups, with intermediate steric demand, give rise to formation of mixtures in ethers but allow switching either to selective CH lithiation in

  （1R）-1,3-Benzazaphospholes 1 ac（吲哚类型的P = CH-NR杂环）与tBuLi发生两种反应，具体取决于N取代基的空间需求和介质的极性。小的N-烷基基团的存在会在2-位诱导CH去质子化，生成杂芳基锂试剂2a和2b，而大体积的N-取代基和非极性溶剂会改变在P = C键处的加成反应性。优选的区域选择性是在磷处的叔丁基化，其对反式加合物3b和3c具有优异的非对映选择性，但是在C2至5b处也观察到了叔丁基化。具有中等空间需求的N-新戊基基团导致在醚中形成混合物，但允许切换为在THF / KOtBu中进行选择性CH锂化或在戊烷中进行加成。更大的N-金刚烷基总是引起优选的加成。使用质子化，甲硅烷基化和羧化将P = CLi-NR，（E）-tBuP-CHLi-NR和LiP-CH（tBu）-NR物种转换为相应的sigma（2）-P或sigma（3） ）-P化合物4b和6a，b，
• π-Excess Aromatic σ²P Ligands: Formation of a Heterocyclic 1,2-Diphosphine by the Addition of<i>t</i>BuLi and Subsequent Inverse Addition of the Product at the P=C Bonds of Two Molecules of 1-Neopentyl-1,3-benzazaphosphole
  作者：Bhaskar R. Aluri、Mohammed Ghalib、Markus K. Kindermann、Peter G. Jones、Joachim W. Heinicke

  DOI：10.1002/hc.21277

  日期：2015.11

  N-neopentyl-substituted π-excess P=CH–N heterocycle 1 depends on the solvent (tetrahydrofuran, diethyl ether, hexane, and toluene) and reaction conditions. Trapping of the resulting organolithium compounds with CO2/ClSiMe3, ClSiMe3, or EtI led to various products indicating CH lithiation (1a,b), normal addition of tBuLi at the P=C bond (E/Z-2a,b), inverse addition of the primary addition product 2Li at the P=C bond of

  tBuLi（戊烷）对 N-新戊基取代的 π-过量 P=CH-N 杂环 1 的反应性取决于溶剂（四氢呋喃、乙醚、己烷和甲苯）和反应条件。用 CO2/ClSiMe3、ClSiMe3 或 EtI 捕获所得的有机锂化合物导致各种产物表明 CH 锂化 (1a,b)，在 P=C 键处正常添加 tBuLi (E/Z-2a,b)，反向添加在第二个分子 1 的 P=C 键上的主要加成产物 2Li，提供 3-叔丁基-2,2'-双（1,3-苯并氮杂膦）3，或 tBuLi (4b,c) 的反向加成. 3 的形成证明了不对称杂环 1,2-二膦配体的新途径。新化合物的结构解析基于它们的 31P 和 13C NMR 数据，以及确定的化学位移和 P-C 耦合常数，
• Ambident Reactivity of P˭CH‒N‒Heterocycles: Lithiation and Substitution Sites
  作者：Joachim Heinicke、Bhaskar R. Aluri、Basit Niaz、Sebastian Burck、Dietrich Gudat、Mark Niemeyer、Oldamur Holloczki、Laszlo Nyulaszi、Peter G. Jones

  DOI：10.1080/10426507.2010.514486

  日期：2011.3.31

  Benzofused 1H-1,3-azaphospholes are lithiated at the N-atom by tBuLi but phosphinylation takes place at either the N- or the P-atom. Smaller chlorophosphines react at nitrogen, bulkier react at phosphorus. Substituents at C2 promote the latter mode. N- Substituted 2H-1,3-benzazaphospholes undergo CH-metalation or addition at the P=C bond, depending on the conditions, and allow access to 2-functionally substituted benzazaphospholes or their 2,3-dihydro derivatives, new sigma P-2,X or sigma P-3,X hybrid ligands (X=O,P).