| 153956-41-3

• CAS: 153956-41-3；154006-92-5
• 化学式: C₃₂H₃₉MoO₃P₃
• 分子量: 660.521
• InChiKey: DQOPWRQKZGQPHR-UHYBXUTMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  tris(acetonitrile)tricarbonylmolybdenum(0) 、 ethyl-[3-[ethyl(phenyl)phosphanyl]-2-[[ethyl(phenyl)phosphanyl]methyl]-2-methylpropyl]-phenylphosphane 以 二氯甲烷 为溶剂， 以>99的产率得到
  参考文献：
  名称：

  手性三元配体：模内断裂MeC（CH 2 PPh 2）3 →MeC（CH 2 P（Ph）（R））3；Zwischenstufen，非对映异构体和复合化学

  摘要：

  三脚架配位体H 3 CC（CH 2 PPH 2）3，1，与锂金属反应生成H 3 CC（CH 2 PPhLi）3，2，以良好产率。化合物2个结晶形式的2 · 4 THF·男性（CH 2 CH 2 NME 2）2。该加合物的晶体结构显示出桥连以及锂的末端磷配位。化合物2与亲电试剂RX反应生成H 3 CC（CH 2 P（Ph）（R））3，3（R = H，ME等，我PR，CH 2 PH，3A-3E）。转化1 → 2 → 3可以在一锅反应中进行。尽管手性化合物3可以如此表征，但它们与（CH 3 CN）3 Mo（CO）3的反应产生易于表征的配位化合物H 3 CC（CH 2 P（Ph）（R））3 Mo （CO）3，5。的NMR分析3只5示出了从两个非对映体形式3（对映体对SSR / RRS和对SSS / RRR）仅以R = CH 2 Ph（3e，5e）形成SSR / RRS-非对映异构体。在其他情况下（R

  DOI：

  10.1016/0022-328x(93)80458-n

文献信息

• Diastereoselectivity in the Reaction of RCH ₂ C[CH ₂ P (Ar)(Lr)] ₃ with Electrophiles: Enhancement of Diastereoselective Control by η ³ ‐Coordination in {RCH ₂ C[CH ₂ P(Ar)(Li) ₃ }Mo(Co) ₃
  作者：Michael Büchner、Gottfried Huttner、Ute Winterhalter、Axel Frick

  DOI：10.1002/cber.19971301006

  日期：1997.10

  AbstractFollowing a procedure developed for H3CC[CH2P(Ph)2]3 (1a) as the starting compound, various tripod ligands RCH2C[CH2P(Ar)2]3 (1) have been transformed into the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 with various electrophiles R′ — Hal leads to the two diastereomers of RCH2C[CH2P‐(Ar)(R)]3 (6) with an (RRR/SSS : RRS/SSR) ratio close to the statistical value of 1:3, except when ArPh and R′Bzl, where the RRS/SSR diastereomer is obtained almost exclusively. In contrast, the reaction of [RCH2C[CH2P(Ar)(Li)[3]‐Mo(CO)3 (4) with electrophiles R′ — Hal tends to favour the formation of the homochiral RRR/SSS diastereomers. The triphosphide coordination compounds 4 are available by two different routes: either the complexes (RCH2C[CH2P‐(Ar)(H)]3Mo(CO)3, obtained from 2 and (CH3CN)3Mo(CO)3, are deprotonated by MeLi, or the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 are reacted with (CH3CN)3Mo(CO)3 to produce 4 in high yields. The ration in which the two diastereomeric forms of 5 are obtained depends on the nature of the electrophile: the greatest diastereomeric discrimination is obtained for ArPh, RPh, R′Bzl, where the homochiral relative to the RRS/SSR pair. Two‐dimensional NMR spectra and simulations of one‐dimensional spectra are used to ascertain the diastereomeric excess in each case. X‐ray analyses of three compounds of type 5 (5d, ArPh, RH, R′Ph, R′Bzl) indicate the remarkable conformational stability of the tripod metal scaffolding, with the conformations observed for these three compounds in three different solid‐state environments being closely similar, even with respect to the torsional arrangement of the phosphorus‐bound benzyl groups.