1,5-二苯基戊烷-1,5-二醇 | 5449-44-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 1,5-二苯基戊烷-1,5-二醇
• 英文名称: 1,5-diphenyl-pentane-1,5-diol
• 英文别名: 1,5-diphenyl-1,5-pentanediol；1,5-diphenylpentane-1,5-diol；α.ε-Dioxy-α.ε-diphenyl-pentan；α.α'-Diphenyl-pentamethylenglykol；1,5-Diphenyl-pentan-1,5-diol
• CAS: 5449-44-5
• 化学式: C₁₇H₂₀O₂
• 分子量: 256.345
• InChiKey: DLZYVGAWUPIIFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,5-二苯基戊烷-1,5-二醇 在 platinum(II) chloride silver hexafluoroantimonate 作用下， 以 1,2-二氯乙烷 为溶剂， 以94%的产率得到2,6-diphenyl-tetrahydropyran
  参考文献：
  名称：

  Cationic Platinum-Catalyzed Etherification by Intra- and Intermolecular Dehydration of Alcohols

  摘要：

  双醇的催化醚化反应利用阳离子铂盐生成各种环醚，该阳离子铂盐是由PtCl2和AgSbF6现场制备的。苄醇的醚化反应也可以通过分子间脱水实现。无论是在空气中还是分子内外的醚化反应都能顺利进行。

  DOI：

  10.1055/s-2004-835664
• 作为产物：
  描述：

  肉桂基亚苯乙酮 在 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 Wilkinson's catalyst 、 过氧化氢苯甲酰 、 R-Alpine-Hydride 、 氢气 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 四氯化碳 、 乙醇 、 苯 为溶剂， -100.0~50.0 ℃ 、344.73 kPa 条件下， 反应 17.75h， 生成 1,5-二苯基戊烷-1,5-二醇
  参考文献：
  名称：

  Stereocontrol between Remote Atom Centers in Acyclic Substrates. Anti Addition of Hydride to 1,5-, 1,6-, and 1,7-Hydroxy Ketones

  摘要：

  For conformationally unconstrained, acyclic organic compounds, the control of stereogenic centers at remote positions of a chain, that is, at a distance of four or more atom centers, remains a challenging problem in asymmetric synthesis. We report on our studies of 1,5, 1,6, and 1,7 diastereoselectivity in hydride reductions of acyclic hydroxy amino ketones and related compounds, which were sparked by our discovery of high 1,5 diastereocontrol (>10:1) with substrates such as 17 and 23. We have been able to achieve both high 1,5- and 1,6-anti diastereocontrol in the reduction of 1,5- and 1,6-hydroxy ketone substrates, respectively. However, the level of 1,7-anti diastereocontrol with 1,7-hydroxy ketones was only moderate. More specifically, reduction of 23 to 24 with R-alpine-hydride or Zn(BH4)(2) in CH2Cl2 (predominantly) at -78 degrees C gave high 1,5-anti stereoselectivity (anti/syn = 10:1 or 13:1, respectively), and reduction of 34 to 35 with R-alpine-hydride (CH2Cl2) gave high 1,6-anti selectivity (anti/syn = 12:1, respectively), whereas reduction of 46 to 44 with R-alpine-hydride (CH2Cl2) gave only moderate 1,7-anti stereoselectivity (anti/syn = 3:1). Results for reductions of 1,5- and 1,6-hydroxy ketone substrates having the N-benzyl structural subunit replaced (i.e., 27 --> 28, 29 --> 30, 31 --> 32, 52 --> 53, 54a --> 55a, 54b --> 55b, 54c --> 55c, and 56 --> 57) clearly indicate that the stereoelectronic character of this subunit plays a critical. role in the attainment of high anti asymmetric induction. Thus, while we obtained exceptionally high 1,6-anti stereoselectivity in the reduction of the N-mesitylmethyl substrate, 54c, to 1,6-diols 55c (anti/syn = 22:1) with R-alpine-hydride at -78 degrees C in CH2Cl2, the N-methyl substrate, 54b, gave a relatively modest anti/syn ratio of 3:1. The diminished anti/syn ratio of 4:1 in the R-alpine-hydride reduction of methoxy amino ketone 50 to 51 also indicates the importance of the free hydroxyl group for attaining high 1,6-anti stereoselectivity. To rationalize the high remote anti stereocontrol in such acyclic systems, we discuss a chelation-controlled mechanism, involving external hydride addition to a bicyclic metal complex with a coordinated ketone carbonyl (e.g., 33) vs internal hydride addition to a monocyclic metal complex with an uncoordinated ketone carbonyl (e.g., 58).

  DOI：

  10.1021/jo981341m

文献信息

• Nonclassical Mechanism in the Cyclodehydration of Diols Catalyzed by a Bifunctional Iridium Complex
  作者：Greco González Miera、Aitor Bermejo López、Elisa Martínez‐Castro、Per‐Ola Norrby、Belén Martín‐Matute

  DOI：10.1002/chem.201805460

  日期：2019.2.18

  1,4‐ and 1,5‐diols undergo cyclodehydration upon treatment with cationic N‐heterocyclic carbene (NHC)–IrIII complexes to give tetrahydrofurans and tetrahydropyrans, respectively. The mechanism was investigated, and a metal‐hydride‐driven pathway was proposed for all substrates, except for very electron‐rich ones. This contrasts with the well‐established classical pathways that involve nucleophilic

  1,4-和1,5-二醇在用阳离子N-杂环卡宾(NHC)-Ir III络合物处理后发生环化脱水，分别生成四氢呋喃和四氢吡喃。研究了该机制，并提出了一种适用于所有底物的金属氢化物驱动途径，除了电子非常丰富的底物。这与涉及亲核取代的成熟经典途径形成对比。
• Selective Mono Addition of Aryllithiums to Dialdehydes by Micromixing
  作者：Aiichiro Nagaki、Hiroki Yamashita、Yusuke Takahashi、Satoshi Ishiuchi、Keita Imai、Jun-ichi Yoshida

  DOI：10.1246/cl.170899

  日期：2018.1.5

  Micromixing enables highly selective mono addition of aryllithiums to dialdehydes. Because the unchanged formyl group in the products can be used for further transformations, the present approach serves as a powerful method for protecting-group-free synthesis.

  微观混合使得芳基锂对二醛的高度选择性单加成成为可能。由于产物中未变动的醛基可以用于进一步转化，当前方法提供了一种强有力的无保护基团合成手段。
• 用于制备烯烃聚合催化剂的二元磺酸酯化合 物
  申请人：中国石油天然气股份有限公司

  公开号：CN105712909B

  公开（公告）日：2018-07-13

  本发明涉及一种具有下述通式(Ⅰ)所示的用于制备烯烃聚合催化剂的二元磺酸酯化合物。其中，A、B为碳或选自氮、氧、硫、硅、硼、磷的杂原子，R1‑R6、R1‑R2n基团为相同或不相同的氢、卤素或取代或未取代的直链或支链的C1‑C20的烷基、C3‑C20环烷基、C6‑C20芳基、C7‑C20芳烷基或烷芳基、C2‑C20烯烃基、C6‑C20稠环芳基、C1‑C20酯基，R1和R2不是氢，R3‑R6及R1‑R2n基团上任意包含一个或几个杂原子作为碳或氢原子或两者的取代物，所述的杂原子选自氮、氧、硫、硅、硼、磷或卤原子，R3‑R6及R1‑R2n基团中的一个或多个可以连起来成环；n为0‑10的整数。
• Arene-promoted lithiation of 1,n-dihaloalkanes (n=2–6): a comparative study
  作者：Abdeslam Abou、Francisco Foubelo、Miguel Yus

  DOI：10.1016/j.tet.2006.08.064

  日期：2006.10

  n-dichloroalkanes 3a (n=2–6) with an excess of lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB; 2.5 mol %) in the presence of different carbonyl compounds [ButCHO, PhCHO, Et2CO, (CH2)4CO, (CH2)5CO, (CH2)7CO, (−)-menthone], in THF at −78 °C leads, after hydrolysis with water, to the expected 1,(n+2)-diols 4, yields being <25% for n=2, 3 and in the range of 45–79% for n=4–6. When the

  1，n-二氯烷烃3a（n = 2–6）与过量的锂粉和催化量的4,4'-二叔丁基联苯（DTBB; 2.5 mol％）在不同羰基存在下的反应化合物[卜吨CHO，苯甲醛，等2 CO，（CH 2）4 CO，（CH 2）5 CO，（CH 2）7 CO，（ - ） -薄荷酮]，在THF中在-78℃下引线，后用水水解，以期望的1，（ñ 2）-diols 4，产率是<25％ñ = 2，3和为45-79％的范围内ñ= 4–6。当相同的协议被施加到1，Ñ -bromochloroalkanes 3B和1，Ñ -dibromoalkanes 3C（Ñ = 2-6），二醇4在一般得到较低的产率。
• Nanosecond flash photolysis studies of intersystem crossing rate constants in biradicals: structural effects brought about by spin-orbit coupling
  作者：Matthew B. Zimmt、Charles Doubleday、Ian R. Gould、Nicholas J. Turro

  DOI：10.1021/ja00309a059

  日期：1985.11

  On montre que le couplage spin-orbite est renforce dans les diradicaux ayant un groupe acyle terminal. Effet de la longueur de la chaine et de la conformation

  在 montre que le couplage spin-orbite est renforce dans les diradicaux ayant un groupe acyle 终端。Effet de la longueur de la chaine et de la 构象