(S,S)-BPBP | 959395-07-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (S,S)-BPBP
• 英文别名: (2S,2'S)-1,1'-Bis(pyridin-2-ylmethyl)-2,2'-bipyrrolidine；2-[[(2S)-2-[(2S)-1-(pyridin-2-ylmethyl)pyrrolidin-2-yl]pyrrolidin-1-yl]methyl]pyridine
• CAS: 959395-07-4
• 化学式: C₂₀H₂₆N₄
• 分子量: 322.453
• InChiKey: XMBZMHWNENRJHR-PMACEKPBSA-N

物化性质

• 比旋光度：
  -94.6° (c 1.0, methanol)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  32.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S,S)-BPBP 、 copper(II) bis(trifluoromethanesulfonate) 以81%的产率得到(trans-PDP)Cu(CF3SO3)2
  参考文献：
  名称：

  Topological Variations of the PDP Ligand and Its Prospects in Molybdenum(0) Dearomatization Agents

  摘要：

  The compounds fac-(K-3-PDP)Mo(CO)(3) {1; PDP = 2-[[2-(1-(pyridin-2-ylmethyl)pyrrolidin-2-yl)pyrrolidin-1-yl]methyl]pyridine}, [(cis-beta-PDP)Mo(NO)(CO)] PF6 ([cis-beta-3]PF6), [(cis-alpha-PDP)Mo(NO)(CO)]PF6 ([cis-alpha-3] PF6)[(cis-alpha-PDP)Mo(NO)Br]PF6 ([4]PF6), [(trans-PDP)Cu] (BF4)(2)center dot CH3CN ([5](BF4)(2)center dot CH3CN), and [(trans-PDP)Cu](OSO2CF3)(2) ([5](OSO2CF3)(2)) have been synthesized and structurally characterized by single-crystal X-ray diffraction. These are the first reported complexes of PDP on metal centers other than iron(II). The observed configurations indicate a broader range of accessible PDP topologies than has been reported. The {(cis-alpha-PDP)Mo(NO)}(+) fragment is found to be less pi-basic than the dearomatizing {Tp(MeIm)Mo(NO)} fragment [Tp = hydridotris(1-pyrazolyl)borato; MeIm = 1-methylimidazole].

  DOI：

  10.1021/ic200403t
• 作为产物：
  描述：

  2-氯甲基吡啶盐酸盐 、 2,2-双吡咯烷 在 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 18.0h， 以71%的产率得到(S,S)-BPBP
  参考文献：
  名称：

  锰催化剂对官能化苄基化合物的化学选择性氧官能化

  摘要：

  介绍了一种新型联哌啶基锰催化剂，可在温和条件下、短时间内催化多种不同官能化烷基芳烃的化学选择性苄基氧化，生成多种官能化芳基酮、环状亚胺和生物活性分子。

  DOI：

  10.1002/anie.202205983

文献信息

• Asymmetric Epoxidation with H₂O₂by Manipulating the Electronic Properties of Non-heme Iron Catalysts
  作者：Olaf Cussó、Isaac Garcia-Bosch、Xavi Ribas、Julio Lloret-Fillol、Miquel Costas

  DOI：10.1021/ja4078446

  日期：2013.10.2

  catalyzes highly enantioselective epoxidation of olefins with H2O2 is described. Improvement of enantiomeric excesses is attained by the use of catalytic amounts of carboxylic acid additives. Electronic effects imposed by the ligand on the iron center are shown to synergistically cooperate with catalytic amounts of carboxylic acids in promoting efficient O-O cleavage and creating highly chemo- and

  描述了催化烯烃与 H2O2 的高度对映选择性环氧化的非血红素铁配合物。通过使用催化量的羧酸添加剂来改善对映体过量。配体对铁中心施加的电子效应显示出与催化量的羧酸协同作用，促进有效的 OO 裂解并产生高度化学和对映选择性的环氧化物质，从而以具有合成价值的产率和较短的反应时间提供广泛的环氧化物.
• Making Fe(BPBP)-catalyzed C–H and CC oxidations more affordable
  作者：Vital A. Yazerski、Peter Spannring、David Gatineau、Charlotte H. M. Woerde、Sara M. Wieclawska、Martin Lutz、Henk Kleijn、Robertus J. M. Klein Gebbink

  DOI：10.1039/c3ob42249f

  日期：——

  The limited availability of catalytic reaction components may represent a major hurdle for the practical application of many catalytic procedures in organic synthesis. In this work, we demonstrate that the mixture of isomeric iron complexes [Fe(OTf)2(mix-BPBP)] (mix-1), composed of Λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1), Δ-α-[Fe(OTf)2(R,R-BPBP)] (R,R-1) and Δ/Λ-β-[Fe(OTf)2(R,S-BPBP)] (R,S-1), is a practical catalyst for the preparative oxidation of various aliphatic compounds including model hydrocarbons and optically pure natural products using hydrogen peroxide as an oxidant. Among the species present in mix-1, S,S-1 and R,R-1 are catalytically active, act independently and represent ca. 75% of mix-1. The remaining 25% of mix-1 is represented by mesomeric R,S-1 which nominally plays a spectator role in both C–H and CC bond oxidation reactions. Overall, this mixture of iron complexes displays the same catalytic profile as its enantiopure components that have been previously used separately in sp3 C–H oxidations. In contrast to them, mix-1 is readily available on a multi-gram scale via two high yielding steps from crude DL/meso-2,2′-bipyrrolidine. Next to its use in C–H oxidation, mix-1 is active in chemospecific epoxidation reactions, which has allowed us to develop a practical catalytic protocol for the synthesis of epoxides.

  催化反应组分的有限可用性可能成为许多催化过程在有机合成中实际应用的主要障碍。本工作中,我们证明了由异构铁配合物[Fe(OTf)2(mix-BPBP)] (mix-1)组成的混合物,包括λ-α-[Fe(OTf)2(S,S-BPBP)] (S,S-1)、Δ-α-[Fe(OTf)2(R,R-BPBP)] (R,R-1)和Δ/λ-β-[Fe(OTf)2(R,S-BPBP)] (R,S-1),是使用过氧化氢作为氧化剂对包括模型烃和光学纯天然产物在内的各种脂肪族化合物进行制备氧化的实用催化剂。在mix-1中存在的物种中,S,S-1和R,R-1是催化活性的,独立作用,约占mix-1的75%。剩余的25%由介观R,S-1代表,名义上在C–H和CC键氧化反应中起旁观者作用。总体而言,这种铁配合物混合物显示出与其先前分别用于sp3 C–H氧化的纯对映体组分相同的催化特征。与它们不同的是,mix-1可通过从粗DL/中二吡咯烷的两个高产率步骤大量制备。除了用于C–H氧化外,mix-1在化学选择性环氧化反应中也表现出活性,这使我们能够开发出一种用于环氧化合物合成的实用催化方案。
• CHEMOSELECTIVE METHYLENE HYDROXYLATION IN AROMATIC MOLECULES
  申请人：The Board of Trustees of the University of Illinois

  公开号：US20200087331A1

  公开（公告）日：2020-03-19

  A chemoselective and reactive Mn(CF 3 -PDP) catalyst system that enables for the first time the strategic advantages of late-stage aliphatic C—H hydroxylation to be leveraged in aromatic compounds. This discovery will benefit small molecule therapeutics by enabling the rapid diversification of aromatic drugs and natural products and identification of their metabolites.

  一种化学选择性和反应性的Mn(CF3-PDP)催化体系首次实现了后期脂肪族C—H羟基化在芳香化合物中的战略优势。这一发现将有助于小分子药物的快速多样化和芳香类药物以及天然产物的代谢产物的鉴定。
• Selective Aliphatic C-H Oxidation
  申请人：White M. Christina

  公开号：US20110015397A1

  公开（公告）日：2011-01-20

  A composition including a complex of a metal, a tetradentate ligand, at least one ancillary ligand, and a counterion may be used for selective sp 3 C—H bond oxidation. The tetradentate ligand may include a N-heterocyclic-N,N′-bis(pyridyl)-ethane-1,2-diamine group or a N,N′-bis(heterocyclic)-N,N′-bis(pyridyl)-ethane-1,2-diamine group. The composition can be used in combination with H 2 O 2 to effect highly selective oxidations of unactivated sp 3 C—H bonds over a broad range of substrates. The site of oxidation can be predicted, based on the electronic and/or steric environment of the C—H bond. In addition, the oxidation reaction does not require the presence of directing groups in the substrate.

  一种包括金属复合物、四齿配体、至少一种辅助配体和对离子的组合物可用于选择性氧化sp3C—H键。四齿配体可能包括N-杂环-N,N′-双(吡啶基)-乙烷-1,2-二胺基团或N,N′-双(杂环)-N,N′-双(吡啶基)-乙烷-1,2-二胺基团。该组合物可与H2O2结合使用，对广泛范围的底物进行高度选择性的氧化未活化的sp3C—H键。可以根据C—H键的电子和/或立体环境预测氧化位置。此外，氧化反应不需要底物中存在导向基团。
• Highly efficient epoxidation of vegetable oils catalyzed by a manganese complex with hydrogen peroxide and acetic acid
  作者：Jianming Chen、Marc de Liedekerke Beaufort、Lucas Gyurik、Joren Dorresteijn、Matthias Otte、Robertus J. M. Klein Gebbink

  DOI：10.1039/c8gc03857k

  日期：——

  stabilizers, and surface coating formulations. In this paper, a catalytic protocol for the efficient epoxidation of vegetable oils is presented that is based on a combination of a manganese catalyst, H2O2 as an oxidant, and acetic acid as an additive. This protocol relies on the use of a homogeneous catalyst based on the non-noble metal manganese in combination with a racemic mixture of the N,N′-bis(2-picolyl)-2

  环氧植物油（EVO）是用于润滑剂，增塑剂，聚氯乙烯（PVC）稳定剂和表面涂料配方的多功能构建基块。在本文中，提出了一种有效的植物油环氧化的催化方案，该方案基于锰催化剂，H 2 O 2作为氧化剂和乙酸作为添加剂的组合。该方案依赖于基于非贵金属锰的均相催化剂与N，N'-双（2-吡啶甲基）-2,2'-双吡咯烷配体（rac -BPBP）的外消旋混合物的组合使用。优化的反应条件仅需相对于双键的数量（约1 mol。）的锰催化剂为0.03 mol％。相对于油为0.1重量％）和环境温度。该环氧化方案非常有效，因为它可以使大多数研究过的植物油（包括廉价的废食用油）以90％以上的产率完全环氧化为EVO，并在2小时的反应时间内具有出色的环氧化物选择性（> 90％）。 。另外，该方案在由植物油本身和乙酸水相构成的两相反应介质中进行，可以通过简单的萃取容易地从中分离出环氧化产物。在效率和反应条件方面，当前的环氧化方