(R,R)-2-exo-3-endo-bis(diphenylphosphino)bicyclo-[2.2.1]-heptane

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (R,R)-2-exo-3-endo-bis(diphenylphosphino)bicyclo-[2.2.1]-heptane
• 英文别名: (1R,2R,3R,4S)-2,3-Bis(diphenylphosphaneyl)bicyclo[2.2.1]heptane；[(1R,2R,3R,4S)-3-diphenylphosphanyl-2-bicyclo[2.2.1]heptanyl]-diphenylphosphane
• 化学式: C₃₁H₃₀P₂
• 分子量: 464.527
• InChiKey: LBNIIIAVAIZHKJ-RMDVPPNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  五甲基环戊二烯基双(三苯基膦)氯化钌(II) 、 (R,R)-2-exo-3-endo-bis(diphenylphosphino)bicyclo-[2.2.1]-heptane 以 甲苯 为溶剂， 生成 (η(5)-C5Me5)Ru((R,R)-2-exo-3-endo-bis(diphenylphosphino)bicyclo[2.2.1]heptane)Cl
  参考文献：
  名称：

  Pentamethylcyclopentadienyl ruthenium(II) complexes containing chiral diphospines: synthesis, characterisation and electrochemical behaviour. X-ray structure of (η5-C5Me5)Ru{(S,S)-Ph2PCH(CH3)CH(CH3)PPh2}Cl

  摘要：

  Some pentamethylcyclopentadienyl ruthenium(II) diphosphine chloride complexes have been prepared by ligand exchange starting with the parent triphenylphosphine derivatives and their reactivities compared with those of the corresponding cyclopentadienyl compounds. The pentamethyl ligand causes a greater extent of asymmetric induction when the (R)-prophos and (R)-phenphos ligands are used as well as a higher lability of the stereochemistry at the stereogenic ruthenium centre. A shift of about 200 mV in the oxidation potential is caused by the substitution at the penta-hapto ligand. The order of basicity of the diphosphine ligands was also evaluated and was found to be consistent with previous determinations. The crystal structure of(eta(5)-C5Me5)Ru {(S,S)-chiraphos}Cl shows a coordination around the ruthenium atom similar to that found for the (eta(5)-C5H5)Ru{(S,S) -chiraphos}Cl complex. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(98)00219-9
• 作为试剂：
  描述：

  6-苯基己-5-炔-1-醇 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex (R,R)-2-exo-3-endo-bis(diphenylphosphino)bicyclo-[2.2.1]-heptane 、 苯甲酸 作用下， 以 苯 为溶剂， 反应 72.0h， 生成 (S,E)-2-styryltetrahydrofuran 、 (R,E)-2-styryltetrahydrofuran
  参考文献：
  名称：

  Palladium-Catalyzed Intramolecular Asymmetric Hydroamination, Hydroalkoxylation, and Hydrocarbonation of Alkynes

  摘要：

  A conceptually novel approach for asymmetric intramolecular hydroamination, hydroalkoxylation and hydrocarbonation of alkynes using chiral palladium catalysts are described. The reactions of the aminoalkynes 5, alkynols 7, and alkynylmethines 9 in the presence of Pd-2(dba)(3)center dot CHCl3/PhCOOH/renorphos 4 in benzene (or benzene-hexane) at 100 degrees C gave the corresponding cyclization products (nitrogen heterocycles 6, oxygen heterocycles 8, and carbocycles 10) in good yields with good enantioselectivities. The origins of enantioselectivities in the hydroamination reaction are discussed based on DFT computations.

  DOI：

  10.1021/jo0603835

文献信息

• Morandini, Franco; Pilloni, Giuseppe; Consiglio, Giambattista, Organometallics, 1993, vol. 12, # 9, p. 3495 - 3503
  作者：Morandini, Franco、Pilloni, Giuseppe、Consiglio, Giambattista、Sironi, Angelo、Moret, Massimo

  DOI：——

  日期：——
• Synthesis, characterisation and stereochemistry of indenyl complexes of iridium(I) containing chiral diphosphines
  作者：Franco Morandini、Giambattista Consiglio

  DOI：10.1016/s0020-1693(96)05535-1

  日期：1997.5

  Indenyl iridium(I) complexes of the type (eta(5)-C9H7)Ir(diphos) (diphos=PPh3, dppe, rac-cypenphos, (S,S)-chiraphos, (R)-prophos, (R,R)-renorphos and (R)-phenphos) have been synthesised by reacting (eta(5)-C9H7)Ir(C2H4)(2) with the appropriate diphosphine. The complexes show a dynamic behaviour in solution the energy barrier being in the range 8-13 kcal mol(-1) comparable with that observed for the corresponding rhodium(I) analogues. For complexes in which the diphosphine has a C-1 symmetry, the energy differences between the two diastereomeric conformations that are recognised at low temperature depend on the diphosphine used, not being substantially influenced by the metal centre.
• Pentamethylcyclopentadienyl ruthenium(II) complexes containing chiral diphospines: synthesis, characterisation and electrochemical behaviour. X-ray structure of (η5-C5Me5)Ru{(S,S)-Ph2PCH(CH3)CH(CH3)PPh2}Cl
  作者：Franco Morandini、Anna Dondana、Ingrid Munari、Giuseppe Pilloni、Giambattista Consiglio、Angelo Sironi、Massimo Moret

  DOI：10.1016/s0020-1693(98)00219-9

  日期：1998.11

  Some pentamethylcyclopentadienyl ruthenium(II) diphosphine chloride complexes have been prepared by ligand exchange starting with the parent triphenylphosphine derivatives and their reactivities compared with those of the corresponding cyclopentadienyl compounds. The pentamethyl ligand causes a greater extent of asymmetric induction when the (R)-prophos and (R)-phenphos ligands are used as well as a higher lability of the stereochemistry at the stereogenic ruthenium centre. A shift of about 200 mV in the oxidation potential is caused by the substitution at the penta-hapto ligand. The order of basicity of the diphosphine ligands was also evaluated and was found to be consistent with previous determinations. The crystal structure of(eta(5)-C5Me5)Ru (S,S)-chiraphos}Cl shows a coordination around the ruthenium atom similar to that found for the (eta(5)-C5H5)Ru(S,S) -chiraphos}Cl complex. (C) 1998 Elsevier Science S.A. All rights reserved.