2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-indole | 919119-72-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-indole
• 英文别名: 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-YL)-1H-indole
• CAS: 919119-72-5
• 化学式: C₂₀H₂₉B₂NO₄
• 分子量: 369.077
• InChiKey: PVELYJHNTSSSOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  52.7
• 氢给体数：
  1
• 氢受体数：
  4

安全信息

• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335

反应信息

• 作为反应物：
  描述：

  2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-indole 在 甲醇 、 bismuth(III) acetate 作用下， 以 四氢呋喃 为溶剂， 反应 17.0h， 以82%的产率得到7-吲哚硼酸频那醇酯
  参考文献：
  名称：

  醋酸铋作为二重和三重氮杂吲哚序列原硼烷脱硼的催化剂

  摘要：

  乙酸铋（III）是一种安全，廉价且选择性的顺序原硼酸脱氢促进剂，当与Ir催化的硼化反应结合使用时，可以接触到各种硼化的吲哚。通过选择性地将6-氟吲哚转化为在4-，5-，7-，2,7-，4,7-， 3,5-和2,4,7-位和舒马曲坦的后期功能化。

  DOI：

  10.1021/acs.orglett.6b00356
• 作为产物：
  描述：

  吲哚 、 频那醇硼烷 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 d^tbpy 作用下， 以 正己烷 为溶剂， 反应 4.0h， 以90%的产率得到2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-indole
  参考文献：
  名称：

  7 位 2-取代吲哚的 Ir 催化功能化：氮定向芳香硼化

  摘要：

  2-取代吲哚的 Ir 催化硼酸化选择性地以良好的产率产生 7-硼酸化产物。2-取代吲哚的先前功能化所需的N-保护是不必要的。

  DOI：

  10.1021/ja0631652

文献信息

• Noncovalent Interactions in Ir-Catalyzed C–H Activation: L-Shaped Ligand for Para-Selective Borylation of Aromatic Esters
  作者：Md Emdadul Hoque、Ranjana Bisht、Chabush Haldar、Buddhadeb Chattopadhyay

  DOI：10.1021/jacs.7b04490

  日期：2017.6.14

  An efficient strategy for the para-selective borylation of aromatic esters is described. For achieving high para-selectivity, a new catalytic system has been developed modifying the core structure of the bipyridine. It has been proposed that the L-shaped ligand is essential to recognize the functionality of the oxygen atom of the ester carbonyl group via noncovalent interaction, which provides an unprecedented

  描述了一种用于芳族酯的对位选择性硼化的有效策略。为了获得高的对位选择性，已经开发了一种新的催化体系，该体系改变了联吡啶的核心结构。有人提出，L型配体对于通过非共价相互作用识别酯羰基的氧原子的功能至关重要，这为超选择性C–H活化/硼化提供了空前的控制因素。
• Iridium‐Catalyzed Ligand‐Controlled Remote <i>para</i> ‐Selective C−H Activation and Borylation of Twisted Aromatic Amides
  作者：Md Emdadul Hoque、Ranjana Bisht、Anju Unnikrishnan、Sayan Dey、Mirja Md Mahamudul Hassan、Saikat Guria、Rama Nand Rai、Raghavan B. Sunoj、Buddhadeb Chattopadhyay

  DOI：10.1002/anie.202203539

  日期：2022.7.4

  A highly para-selective C−H borylation of aromatic amides is reported. The para borylation proceeds via an unprecedented substrate–ligand distortion between the twisted aromatic amides and a newly designed ligand framework (defa), which is different from the standard borylation ligand. A new type of catalytic system was developed by using this defa ligand that demonstrated excellent levels of para

  报道了芳族酰胺的高度对位选择性 C-H 硼基化。对位硼化通过扭曲的芳香酰胺和新设计的配体框架（defa）之间前所未有的底物-配体扭曲进行，这与标准的硼化配体不同。使用这种 defa 配体开发了一种新型催化系统，该配体对一系列芳族酰胺表现出优异的对位选择性。
• Iridium-Catalyzed, Silyl-Directed Borylation of Nitrogen-Containing Heterocycles
  作者：Daniel W. Robbins、Timothy A. Boebel、John F. Hartwig

  DOI：10.1021/ja1006405

  日期：2010.3.31

  Selective methods for the functionalization of indoles and other nitrogen heterocycles would provide access to the core structures of many natural products and pharmaceuticals. Although there are many methods and strategies for the synthesis of substituted indoles or functionalization of the azole ring, strategies for the selective functionalization of the benzo-fused portion of the indole skeleton, particularly the 7-position, are less common. We report a one-pot, iridium-catalyzed, silyl-directed C-H borylation of indoles at the 7-position. This process occurs in high yield with a variety of substituted indoles, and conversions of the 7-borylindole products to 7-aryl-, 7-cinnamyl-, and 7-haloindoles are demonstrated. The Ir-catalyzed, silyl-directed C-H borylation also occurs with several other nitrogen heterocycles, including carbazole, phenothiazines, and tetrahydroquinoline. The utility of this methodology is highlighted by the one-pot synthesis of a member of the pyrrolophenanthridone class of alkaloid natural products.
• Ir-Catalyzed Functionalization of 2-Substituted Indoles at the 7-Position:  Nitrogen-Directed Aromatic Borylation
  作者：Sulagna Paul、Ghayoor A. Chotana、Daniel Holmes、Rebecca C. Reichle、Robert E. Maleczka,、Milton R. Smith

  DOI：10.1021/ja0631652

  日期：2006.12.1

  Ir-catalyzed borylation of 2-substituted indoles selectively yields 7-borylated products in good yields. N-Protection, required for previous functionalizations of 2-substituted indoles, is unnecessary.

  2-取代吲哚的 Ir 催化硼酸化选择性地以良好的产率产生 7-硼酸化产物。2-取代吲哚的先前功能化所需的N-保护是不必要的。
• Bismuth Acetate as a Catalyst for the Sequential Protodeboronation of Di- and Triborylated Indoles
  作者：Fangyi Shen、Sriram Tyagarajan、Damith Perera、Shane W. Krska、Peter E. Maligres、Milton R. Smith、Robert E. Maleczka

  DOI：10.1021/acs.orglett.6b00356

  日期：2016.4.1

  Bismuth(III) acetate is a safe, inexpensive, and selective facilitator of sequential protodeboronations, which when used in conjunction with Ir-catalyzed borylations allows access to a diversity of borylated indoles. The versatility of combining Ir-catalyzed borylations with Bi(III)-catalyzed protodeboronation is demonstrated by selectively converting 6-fluoroindole into products with Bpin groups at

  乙酸铋（III）是一种安全，廉价且选择性的顺序原硼酸脱氢促进剂，当与Ir催化的硼化反应结合使用时，可以接触到各种硼化的吲哚。通过选择性地将6-氟吲哚转化为在4-，5-，7-，2,7-，4,7-， 3,5-和2,4,7-位和舒马曲坦的后期功能化。