(RS,RS)-2,2'-bipiperidine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (RS,RS)-2,2'-bipiperidine
• 英文别名: d,l-2,2'-Dipiperidyl；rac-2,2'-bipiperidine；(+/-)-2,2'-bipiperidine；(+/-)-bip；(2S)-2-[(2S)-piperidin-2-yl]piperidine
• 化学式: C₁₀H₂₀N₂
• 分子量: 168.282
• InChiKey: CLBJZAWCBRAMRZ-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  dichlorobis(dimethyl sulfoxide)platinum(II) 、 (RS,RS)-2,2'-bipiperidine 以 甲醇 为溶剂， 以80%的产率得到[PtCl2((+/-)-bip)]
  参考文献：
  名称：

  能够使鸟嘌呤配位碱基的Pt-N7旋转减慢十亿倍的顺铂类似物的NMR和X射线结构表征：2,2'-联哌啶（二甲基丙二酸）铂（II）络合物。

  摘要：

  报道了顺铂类似物的合成及其NMR和X射线结构表征，旨在将协调的鸟嘌呤碱基的Pt-N7旋转降低十亿倍。[Pt（dmm）{（+/-）-bip}]（dmm =二甲基丙二醛； bip = 2,2'-联哌啶）络合物在C2 / m空间群中结晶，该空间群将bip和dmm分为两等分的镜面配体。因为bip部分（在2,2'-碳原子上的R，R或S，S构型）没有对称平面，所以由R，R的bip分子构成的统计无序满足了晶体对称性的要求。或S，S构型在同一晶体学位置交替出现。bip配体的“准平面性” [通过C和N原子的平均平面的最大偏差为0.2927（9）A]允许这种意外的安排，这样可以将不同手性的Bip分子容纳在同一空间中。重原子的bip阵列从两侧被一层“准轴向”（C）H和（N）H原子（每侧六个）覆盖。一侧的那些氢键合到成对连接的另一个复杂分子的dmm氧原子上。平均铂配位平面之间的距离短至3.498（1）A，可与[PtCl

  DOI：

  10.1021/ic800230p
• 作为产物：
  描述：

  2,2-双哌啶 在 盐酸 作用下， 以 水 、 苯 为溶剂， 反应 1.92h， 生成 (RS,RS)-2,2'-bipiperidine
  参考文献：
  名称：

  手性磷酰胺催化的烯丙基三氯硅烷对醛的对映选择性加成。用二齿磷基酰胺进行的制备性研究

  摘要：

  基于机械学的见解，即对映选择性烯丙基化的速率和立体化学决定步骤涉及多个路易斯基本部分（磷酰胺），开发了二齿手性磷酰胺。通过不同长度的亚甲基链的束缚连接不同的手性磷酰胺部分。发现由二齿磷酰胺促进的与烯丙基三氯硅烷的烯丙基化的速率和对映选择性高度依赖于系链长度。设计了一种新的基于2,2'-双吡咯烷骨架的磷酰胺，在烯丙基化反应中具有良好的收率，有效的转化率和高的对映选择性。对映体纯的2,2'-双吡咯烷的合成很容易通过吡咯烷的光二聚化，然后用四氢呋喃进行拆分而大规模完成。l（或d）酒石酸。用各种取代的烯丙基三氯硅烷和不饱和醛检查了烯丙基化反应的范围。通过添加不对称的γ-二取代的烯丙基三氯硅烷，该方法已应用于立体异构的季中心的构建。

  DOI：

  10.1021/jo052203h

文献信息

• Enantioselective Organocatalytic Michael Addition of Aldehydes to β-Nitrostyrenes
  作者：Marju Laars、Kerti Ausmees、Merle Uudsemaa、Toomas Tamm、Tõnis Kanger、Margus Lopp

  DOI：10.1021/jo900322h

  日期：2009.5.15

  derivatives as organocatalysts in the Michael addition of enamine intermediates formed from aldehydes to nitroolefins has been demonstrated. The best results were obtained when the reaction was run in the presence of (2R,2′R)-N-iPr-bipiperidine. The products were formed via an enamine intermediate with high diastereo- and enantioselectivity with relatively short reaction times.

  已经证明了C 2对称的双哌啶和双吗啉衍生物作为有机催化剂在由醛形成的烯胺中间体的迈克尔加成到硝基烯烃中的用途。当反应在（2存在下运行，获得了最好的结果- [R，2' - [R - ）ñ -iPr联哌啶。产物是通过具有较高的非对映选择性和对映选择性的烯胺中间体，且反应时间较短而形成的。
• Optical resolution of<scp>DL</scp>-2,2′-bipiperidine through its cobalt(<scp>III</scp>) complex
  作者：Mitsunobu Sato、Yoichi Sato、Shigenobu Yano、Sadao Yoshikawa

  DOI：10.1039/dt9850000895

  日期：——

  The separation of racemic 2,2′-bipiperidine and the meso form has been performed through the dihydrochloride salt of the diamine. The reaction of racemic 2,2′-bipiperidine with [Co(NO2)6]3– has been shown to yield only one DL pair of trans-bis(2,2′-bipiperidine)dinitrocobalt(III) complexion. The dinitro-complex has been characterized and optically resolved using ammonium D-2- bromo-4,7-dimethyl-3-oxobicyclo[2

  外消旋的2,2'-联哌啶和内消旋形式的分离已通过二胺的二盐酸盐进行。外消旋2,2'-联哌啶与[Co（NO 2）6 ] 3–的反应已显示仅产生一对DL的反-双（2,2'-联哌啶）二硝基钴（III）络合物。已经使用D -2-溴-4,7-二甲基-3-氧代双环[2.2.1]庚烷-7-甲磺酸铵铵表征并光学拆分了二硝基配合物。光学纯的（–）589从不太溶解的非对映异构体中回收了-2,2'-联哌啶，其比旋度为–12.2°。关于应变能最小化计算的预测，讨论了反式-二硝基配合物的立体选择性形成。
• Chemoselective Oxyfunctionalization of Functionalized Benzylic Compounds with a Manganese Catalyst
  作者：Jimei Zhou、Minxian Jia、Menghui Song、Zhiliang Huang、Alexander Steiner、Qidong An、Jianwei Ma、Zhiyin Guo、Qianqian Zhang、Huaming Sun、Craig Robertson、John Bacsa、Jianliang Xiao、Chaoqun Li

  DOI：10.1002/anie.202205983

  日期：2022.7.25

  A new bipiperidine-based manganese catalyst is introduced, which catalyzes the chemoselective benzylic oxidation of a wide range of diverse functionalized alkyl arenes with H2O2, affording various functionalized aryl ketones, cyclic imines, and bioactive molecules under mild conditions in a short time.

  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。
• A Novel Head-to-Head Conformer of d(GpG) Cross-linked by Pt:  New Light on the Conformation of Such Cross-links Formed by Pt Anticancer Drugs
  作者：Susan O. Ano、Francesco P. Intini、Giovanni Natile、Luigi G. Marzilli

  DOI：10.1021/ja9805674

  日期：1998.11.1

  The critical DNA lesion accounting for the anticancer activity of cis-PtCl2(NH3)(2) and its analogues [CiS-PtX(2)A(2): A(2) = a diamine or two amines, X-2 = anionic leaving ligand(s)] is an unusual intrastrand cis-Pt(d(GpG))A(2) cross-link with Pt linking N7's of adjacent guanines (G). The only known cross-link form with two anti G's, HH1, has head-to-head (HH) bases. We provide NMR, HPLC, and mass spectral evidence for a second, distinct HH cis-Pt(d(GpG))A(2) cross-link conformer, HH2, in BipPt(d(GpG)) (Bip = 2,2'-bipiperidine, where the coordinated Bip has R, S, S, and R configurations at the asymmetric N, C, C, and N chelate ring atoms). The HH1 and HH2 BipPt(d(GpG)) conformers are formed both kinetically and thermodynamically in comparable amounts. The NMR results showed for both BipPt(d(GpG)) conformers that the bases were anti, anti HH, the 5'-G sugar pucker was N, and the 3'-G sugar pucker was S. The major difference between the HH1 and HH2 conformers is the propagation direction of the phosphodiester linkage. Molecular modeling calculations with NMR restraints on the HH1 and HH2 conformers indicate comparable energies and no unusual features that should have precluded prediction of the existence of the HH2 conformer. Calculations led to similar conclusions for the cis-Pt(d(GpG))(NH3)(2) HH2 conformer. During the two decades of intense interest in this cross-link, this new form has gone unrecognized, although published results have suggested the presence of unknown conformers. Our results in this first report of a second anti, anti HH d(GpG) adduct place an entirety different perspective on the conformational diversity of cis-Pt(d(GpG))(NH3)(2) in solution. Although the new HH2 conformation is unlikely to exist in a duplex at low temperature, the new form may be important in mutational events, in duplex breathing, or in duplex interactions with DNA damage recognition proteins and repair enzymes. Finally, the spectral features, especially the H8 NMR signals, of HH1 d(GpG) species in single strands and in duplexes are typically very different, results attributed to differences in both extent and direction of base canting. Bip is an example of a chirality controlling chelate (CCC) ligand that can influence canting. The HH1 conformer of BipPt(d(GpG)) is the first single-stranded species that has key spectral characteristics very similar to those of a typical duplex cross-linked species. Thus, even the HH1 conformer of BipPt(d(GpG)) is an unusual species.