(1R,1'R)-(1,3-phenylenebis(methylene))bis(tert-butyl(phenyl)phosphine borane) | 404849-81-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,1'R)-(1,3-phenylenebis(methylene))bis(tert-butyl(phenyl)phosphine borane)
• 英文别名: (R,R)-(C6H4-2,6-(CH2PPhBu-tBH3)2)；[[3-[(Boranuidyl-tert-butyl-phenylphosphaniumyl)methyl]phenyl]methyl-tert-butyl-phenylphosphaniumyl]boranuide
• CAS: 404849-81-6
• 化学式: C₂₈H₄₂B₂P₂
• 分子量: 462.211
• InChiKey: MAAOTBZIHDYINB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.53
• 重原子数：
  32
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,1'R)-(1,3-phenylenebis(methylene))bis(tert-butyl(phenyl)phosphine borane) 在 四氢吡咯 作用下， 反应 12.0h， 生成 1,3-{bis[(tert-butyl)(phenyl)phosphino]methyl}benzene
  参考文献：
  名称：

  Development of the First P-Stereogenic PCP Pincer Ligands, Their Metallation by Palladium and Platinum, and Preliminary Catalysis

  摘要：

  The potentially tridentate P-stereogenic [P*CP*] ligands 1,3-{bis[(tert-butyl)(phenyl)phosphino]methyl}-benzene and 1,3-[bis[(tert-butyl)(phenyl) phosphino]methyl]-2-bromobenzene have been synthesized as the protected phosphine-borane adducts. Deprotection with a secondary amine affords the free phosphine ligand which can be metallated by Pd and Pt with standard metal synthons. Two of the resultant [P*CP*] metal complexes have been characterized by X-ray crystallography. The complexes exhibit a C-2-symmetric environment about the remaining binding site of the square-planar center, with t-Bu groups filling two quadrants of the open site. The Pd complexes can be converted by use of a Ag salt to the analogous aquo complex, which is catalytically active in the aldol condensation of methyl 2-isocyanoacetate and benzaldehyde. Preliminary results and comparisons with previously reported catalysts with more distal C-stereogenicity are presented.

  DOI：

  10.1002/1522-2675(20011114)84:11<3519::aid-hlca3519>3.0.co;2-9
• 作为产物：
  描述：

  1,3-phenylenebis(methylene) tetraethyl bis(phosphate) 在 rubidium carbonate 、 tris-(dibenzylideneacetone)dipalladium(0) 、 lithium aluminium tetrahydride 、 C₃₆H₄₄NOPS 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙腈 为溶剂， 反应 95.0h， 生成 (1R,1'R)-(1,3-phenylenebis(methylene))bis(tert-butyl(phenyl)phosphine borane)
  参考文献：
  名称：

  钯/Xiao-Phos-催化动力学拆分仲膦氧化物的 P-苄基化

  摘要：

  设计了通过钯/Xiao-Phos 催化的对映选择性P-苄基化过程对外消旋仲膦氧化物的动力学拆分。既，叔-和仲-膦氧化物以良好的收率和对映体纯度优异（选择性因数高达226.1）被交付。几种P-手性化合物、双齿配体的前体和过渡金属配合物的简便制备进一步证明了合成效用。

  DOI：

  10.1002/anie.202111957

文献信息

• Enantioselective synthesis of platinum group metal complexes with the chiral PCP pincer ligand R,R-{C6H4-2,6-(CH2P*PhBut)2}. The crystal structure of R,R-PdCl{C6H3-2,6-(CH2P*PhBut)2}
  作者：David Morales-Morales、Roger E. Cramer、Craig M. Jensen

  DOI：10.1016/s0022-328x(02)01371-2

  日期：2002.7

  The novel PCP chiral ligand R,R-C6H4-2,6-(CH2P*PhBut)2} and its platinum metal complexes have been easily synthesized in enantiomeric pure form. The palladium compound R,R-PdClC6H3-2,6-(CH2P*PhBut)2} has been characterized by X-ray crystal structure analysis thus confirming the absolute configuration of the complexated ligand. Preliminary catalytic experiments with the iridium and palladium complexes

  新颖PCP手性配体- [R ，- [R - C 6 H ^ 4 -2,6-（CH 2 P * PhBu吨）2 }和其铂金属络合物对映体纯的形式被容易地合成的钯化合物。[R ，- [R -通过X射线晶体结构分析表征了PdCl C 6 H 3 -2，6-（CH 2 P * PhBu t）2 }，从而证实了络合配体的绝对构型。铱和钯配合物R，R的初步催化实验-IrH 4 C 6 H ^ 3 -2,6-（CH 2 P * PhBu吨）2 }和[R ，- [R -PdCl C 6 H ^ 3 -2,6-（CH 2 P * PhBu吨）2 }在分别进行了环烷烃的脱氢和苯乙烯的氢化硅烷化，烯丙基烷基化和Heck偶联反应。
• Novel P-Stereogenic PCP Pincer-Aryl Ruthenium(II) Complexes and Their Use in the Asymmetric Hydrogen Transfer Reaction of Acetophenone
  作者：Serenella Medici、Marcella Gagliardo、Scott?B. Williams、Preston?A. Chase、Serafino Gladiali、Martin Lutz、Anthony?L. Spek、Gerard?P.?M. van?Klink、Gerard van?Koten

  DOI：10.1002/hlca.200590048

  日期：2005.3

  ([RuCl(PCP)(PPh3)]) 4c,d were synthesized via transcyclometalation reactions by mixing equivalent amounts of [1,3-phenylenebis(methylene)]bis[diisopropylphosphine] (2c) or [1,3-phenylenebis(methylene)]bis[diphenylphosphine] (2d) and the N-donor pincer-aryl complex [RuCl2,6-(Me2NCH2)2C6H3}(PPh3)], (3; Scheme 2). The same synthetic procedure was successfully applied for the preparation of novel chiral P-donor pincer-aryl

  非手性P-施主钳芳基的钌络合物（将[RuCl（PCP）（PPH 3）]）4c中，d被合成经由通过混合等量的[1,3-亚苯基双（亚甲基）] transcyclometalation反应双[diisopropylphosphine]（2C）或[1,3-亚苯基双（亚甲基）]双[二苯基膦]（2d）和N-施主钳-芳基络合物[RuCl 2,6-（Me 2 NCH 2）2 C 6 H 3 }（PPh 3）]，（3 ;方案2）。通过使P-立体生成的钳形芳烃（S，S）反应，成功地将相同的合成方法用于制备新型手性P-供体钳-芳基钌络合物[RuCl（P * CP *）（PPh 3）] 4a，b。-[[1,3-亚苯基双（亚甲基）]双[（烷基）（苯基）膦] 2a，b（烷基= i Pr或t Bu，P * CHP *）和络合物[RuCl 2,6-（Me 2 NCH 2）2 C 6 H 3 }（PPh 3）]，（3；
• Alkylation of Phosphine Boranes by Phase-Transfer Catalysis
  作者：Hélène Lebel、Sébastien Morin、Valérie Paquet

  DOI：10.1021/ol0347139

  日期：2003.6.1

  [GRAPHICS]The alkylation of phosphine boranes with various electrophiles proceeds with good to excellent yields in a biphasic solution in the presence of tetrabutylammonium bromide as a phase-transfer catalyst.