trans-1,2-bis(dichlorophosphino)cyclopentane | 88293-05-4

• 分子结构分类: 有机化合物 - 有机磷化合物 - 烷基卤代膦
• 英文名称: trans-1,2-bis(dichlorophosphino)cyclopentane
• 英文别名: dichloro-[(1S,2S)-2-dichlorophosphanylcyclopentyl]phosphane
• CAS: 88293-05-4；97714-71-1
• 化学式: C₅H₈Cl₄P₂
• 分子量: 271.878
• InChiKey: PISQAMILQYKMAJ-WHFBIAKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 危险等级：
  8
• 危险品运输编号：
  UN 2920

反应信息

• 作为反应物：
  描述：

  trans-1,2-bis(dichlorophosphino)cyclopentane 在 盐酸 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 0.17h， 生成
  参考文献：
  名称：

  Homochiral cyclopentane-based C1-symmetric P,P ligands C5H8(PPh2)(PR2) from C2-symmetric C5H8(PCl2)2

  摘要：

  Treatment of 1,2-trans-C5H8(PCl2)(2) with 1,2-C2H4(NHPr-i)(2) gave the C-2-symmetric perhydro-1,6,2,5-diazaphosphocine C5H8{P(Cl)N(Pr-i)CH2}(2)-cyclo, which produced dissymmetric C5H8(PPh2){P[N(Pr-i)CH2](2)-cyclo} on further reaction with PhMgBr. Cleavage of the P-N bonds with gaseous HCl afforded C5H8(PPh2)(PCl2), which was converted to C5H8(PPh2){P(OPh)(2)}(2) by reaction with phenol. All chiral P,P derivatives were obtained as racemates as well as resolved (1R,2R)-and (1S,2S)-enantiomers. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2003.10.071
• 作为产物：
  描述：

  (1S,2S)-1,2-Bisphosphanylcyclopentane 在 三光气 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 以66%的产率得到trans-1,2-bis(dichlorophosphino)cyclopentane
  参考文献：
  名称：

  (1S,2S)-Cyclopentane-1,2-diyl-bis(phosphonous dichloride), (1S,2S)-C5H8(PCl2)2 – A Versatile Optically Active Reagent

  摘要：

  DOI：

  10.1002/(sici)1099-0682(199807)1998:7<885::aid-ejic885>3.0.co;2-6

文献信息

• Enantioselective Catalysis; 130: Optically Active Expanded Ligands Based on the trans-1,2-Substituted Cyclopentane Skeleton
  作者：Henri Brunner

  DOI：10.1055/s-1999-3597

  日期：1999.10

  New expanded bisphosphane ligands with a chiral trans-1,2-substituted cyclopentane skeleton were prepared. Polyaldehydes were accessible by coupling optically active bisphosphane precursors with branched aryl bromides. Optically active expanded ligands were obtained by condensation of the aldehydes with chiral amines and amino alcohols. The optically active ligands were tested in several model reactions of enantioselective catalysis, including allylic alkylation, hydrogenation (adopted to the use of water), and hydrosilylation.

  新扩展的双膦配体具有手性反式-1,2-取代环戊烷结构被制备出来。通过将光学活性的双膦前体与支链芳基溴化物偶联，可以获得多醛。通过将醛与手性胺和氨基醇缩合，获得了光学活性扩展配体。光学活性配体在多个手性选择性催化的模型反应中进行了测试，包括烯丙基烷基化、氢化（适用于水的使用）和氢硅化。
• Chirale Bisphosphane IX. Kationische Rhodium(I)-Komplexe mit (1S,2S)-Cyclopentan-1,2-diyl-bis(dialkylphosphan)-Liganden, [(1S,2S)-C5H8(PR2)2Rh(1,5-COD)]O3SCF3: Synthesen, Strukturen und katalytische Anwendungen
  作者：Lutz Dahlenburg、Volker Kurth

  DOI：10.1016/s0022-328x(99)00243-0

  日期：1999.8

  (2) by Grignard substitution. Combination of (1S,2S)-C5H8P(Cl)C8H15-cyclo}2 (4) with CH3MgBr or of (1S,2S)-C5H8P(H)C8H15-cyclo}2 (3) with n-C4H9Li and CH3I afforded (1S,2S)-C5H8P(CH3)C8H15-cyclo}2 (9) as diastereomeric mixtures containing the SP,SP', RP,RP', and RP,SP' stereoisomers 9a–c in different proportions. The optically active chelate ligands 5–9 reacted with [Rh(1,5-COD)2]O3SCF3 to give cationic

  在烯丙醇或1,4-戊二烯中自由基引发的P-H（1 S，2 S）-C 5 H 8（PH 2）2（1）的加成产生了全烷基化的手性P 2配体（1 S，2 S）-C 5 H ^ 8 P（C 3 H ^ 6 OH）2 } 2（6）和（1小号，2小号）-C 5 H ^ 8（PC 5 ħ 10 -环）2（7）。（1 S，2 S）-C 5 H 8（PR 2）2类型的其他P烷基化双膦，其中PR 2 = P（C 4 H 9 - n）2（5）和P（C 6 H 11 -环）2（8）由（1 S，2 S）-C 5 H 8（PCl 2）2（2）由格利雅（Grignard）替代。（1组合小号，2小号）-C 5 H ^ 8 P（CL）C 8 H ^ 15 -环} 2（4）用CH 3 MgBr或（1小号，2小号）-C 5 H ^ 8 P （H）C 8 H ^ 15 -环} 2（3）与ñ -C 4 ħ 9 Li和CH 3我得到（1小号，2小号）-C
• A new route to chiral bis-tertiary phosphine ligands: synthesis, resolution, and crystal structure of trans-bis-1,2-(diphenylphosphino)-cyclopentane and the nickel adduct NiBr2[trans-1,2-(PPh2)2C5H8]
  作者：David L. Allen、Vernon C. Gibson、Malcolm L. H. Green、James F. Skinner、Jim Bashkin、Peter D. Grebenik

  DOI：10.1039/c39830000895

  日期：——

  Heating of white phosphorus, phosphorus trichloride, and cyclopentene at 220 °C gives trans-1,2-bis (dichlorophosphino)cyclopentane (1), which with phenylmagnesium bromide gives trans-1,2-bis(diphenylphosphino)-cyclopentane (dpcp)(2); compound (2)forms the adduct Ni(dpcp) Br2·CH2Cl2, which readily crystallizes as a conglomerate and the pure enantiomers may be separated by hand allowing resolution of

  在220°C下加热白磷，三氯化磷和环戊烯，得到反式-1,2-双（二氯膦基）环戊烷（1），与苯基溴化镁一起得到反式-1,2-双（二苯基膦基）-环戊烷（dpcp） （2）; 化合物（2）形成加合物Ni（dpcp）Br 2 ·CH 2 Cl 2，其易于结晶成团块，可以用手分离纯对映异构体，从而拆分出（2），并进行甲基（N-苯甲酰基）的催化加氢）脱氢苯丙氨酸使用拆分（2）和铑催化剂得到的氢化产物的光学纯度为100％。
• Process for the production of trans-1,2-(dihalophosphino) cycloalkanes
  申请人：The British Petroleum Company p.l.c.

  公开号：EP0117156A1

  公开（公告）日：1984-08-29

  The invention relates to novel trans-1,2-bis(dihalo- phosphino)-cycloalkanes (I) wherein the alkane moiety contains from 3 to 12 carbon atoms, trans-1,2-bis[di(X)-phosphino]cycloalkanes (II) wherein the alkane moiety contains from 3 to 12 carbon atoms and X is either hydrocarbyl or alkoxy and the resolved enantiometers of (II). Compounds (I) are produced by reacting a C3 to C12 cyclic olefin with a trivalent phosporous compound of the formula PX3 wherein X is chlorine or bromine in the presence of elemental phophorous. Compounds (I) are converted to compounds (II) by reaction with an (X)-containing carbon nucleophile.

  本发明涉及新型反式-1,2-双(二卤代膦基)环烷烃(I)（其中烷基含有 3 至 12 个碳原子）、反式-1,2-双[二(X)-膦基]环烷烃(II)（其中烷基含有 3 至 12 个碳原子，X 为烃基或烷氧基）以及(II)的解析对映体。化合物（I）是通过 C3 至 C12 环状烯烃与式 PX3 的三价多孔化合物（其中 X 为氯或溴）在多孔元素存在下发生反应而制得。化合物(I)通过与含(X)碳亲核物反应转化为化合物(II)。
• Davies, Cathryn E.; Gardiner, Ian M.; Green, Jennifer C., Journal of the Chemical Society, Dalton Transactions, 1985, p. 669 - 684
  作者：Davies, Cathryn E.、Gardiner, Ian M.、Green, Jennifer C.、Green, Malcolm, L. H.、Hazel, Nicholas, J.、et al.

  DOI：——

  日期：——