(R,R)-bis(t-butylmethylphosphino)methane

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (R,R)-bis(t-butylmethylphosphino)methane
• 英文别名: (R,R)-bis(tert-butyl(methyl)phosphino)methane；(R,R)-t-Bu-MiniPHOS；(R)-tert-butyl-[[tert-butyl(methyl)phosphanyl]methyl]-methylphosphane
• 化学式: C₁₁H₂₆P₂
• 分子量: 220.275
• InChiKey: YJGHIDMONLDCCH-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• 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

反应信息

• 作为反应物：
  描述：

  (R,R)-bis(t-butylmethylphosphino)methane 在 双氧水 作用下， 以 甲苯 为溶剂， 生成 (S,S)-1,1-bis(tert-butylmethylphosphinyl)methane
  参考文献：
  名称：

  P-手性二氧化膦的合成及其在催化不对称Diels-Alder反应中的应用

  摘要：

  新的P-手性氧化膦，（R，R）-1,2-双（烷基甲基膦基）乙烷（烷基= 1-金刚烷基，叔丁基）和（S，S）-1,1-双（叔丁基甲基次膦基）甲烷通过四个步骤从PCl 3合成。它们的铁（III）络合物可有效地催化N-丙烯酰胺双亲亲烯的不对称Diels-Alder反应，提供高达75％的对映选择性。

  DOI：

  10.1016/s0040-4039(00)01030-3
• 作为产物：
  描述：

  (S)-tert-butylmethylphosphine-borane 在 正丁基锂 、 tetrafluoroboric acid diethyl ether 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.42h， 生成 (R,R)-bis(t-butylmethylphosphino)methane
  参考文献：
  名称：

  旋光性二级膦-硼烷的利用：铑催化的不对称氢化中P-手性二膦的合成及其对映体诱导能力

  摘要：

  叔丁基甲基膦-硼烷的两种对映体均已用于合成手性二膦和/或其硼烷配合物。1,2-双（叔丁基甲基膦基）乙烷的对映体硼烷络合物（t -Bu-BisP ∗）是由仲膦-硼烷和1,2-二氯乙烷高收率制备的。制备了t -Bu-MiniPHOS的单螯合Rh络合物，并在某些代表性官能化烯烃的不对称加氢中检测了其催化活性。还描述了具有喹啉或喹喔啉骨架的三个新的P-手性膦配体的合成及其对映体诱导能力。

  DOI：

  10.1016/j.tet.2015.05.088
• 作为试剂：
  描述：

  diethylzinc 、 苯亚甲基苯乙酮 在 copper(II) bis(trifluoromethanesulfonate) 、 (R,R)-bis(t-butylmethylphosphino)methane 作用下， 以 甲苯 为溶剂， 反应 24.0h， 生成 (E)-(S)-1,3-Diphenyl-pent-1-en-3-ol 、
  参考文献：
  名称：

  亚甲基桥连的P-手性二膦类化合物的高度对映选择性反应。

  摘要：

  DOI：

  10.1021/jo990131m

文献信息

• Optically Active Dinuclear Palladium Complexes Containing a Pd−Pd Bond: Preparation and Enantioinduction Ability in Asymmetric Ring-Opening Reactions
  作者：Tomokazu Ogura、Kazuhiro Yoshida、Akira Yanagisawa、Tsuneo Imamoto

  DOI：10.1021/ol900533h

  日期：2009.6.4

  Optically active dinuclear palladium complexes containing a Pd−Pd bond were prepared by using (R,R)-bis(tert-butylmethylphosphino)methane ((R,R)-t-Bu-MiniPHOS). The dinuclear palladium complexes coupled with silver triflate exhibited good to excellent enantioselectivities up to 99% in palladium-catalyzed alkylative ring-opening reactions of azabenzonorbornadienes.

  通过使用（R，R）-双（叔丁基甲基膦基）甲烷（（R，R）-t -Bu-MiniPHOS）制备包含Pd-Pd键的旋光性双核钯配合物。在三氮杂苯并降冰片二烯的钯催化的烷基化开环反应中，双核钯配合物与三氟甲磺酸银偶联显示良好至优异的对映选择性，高达99％。
• METHOD FOR PRODUCING OPTICALLY ACTIVE 3-AMINOCARBOXYLIC ACID ESTERS
  申请人：Jaekel Christoph

  公开号：US20090299089A1

  公开（公告）日：2009-12-03

  The invention relates to a method for producing optically active 3-aminocarboxylic acid ester compounds. According to said method, an enantiomer mixture of a mono-N-acylated 3-aminocarboxylic acid ester, which mixture was previously enriched in an enantiomer, is subjected to deacylation and then to a further enantiomer enrichment by crystallization by adding an acidic salt-forming substance.

  本发明涉及一种生产光学活性3-氨基羧酸酯化合物的方法。根据该方法，先将单N-酰化的3-氨基羧酸酯的对映体混合物在对映体富集后，经脱酰化处理，再通过添加酸性盐形成物结晶进行进一步的对映体富集。
• Asymmetric Hydrogenation Catalyzed by (S,S)-R-BisP*-Rh and (R,R)-R-MiniPHOS Complexes: Scope, Limitations, and Mechanism
  作者：Ilya D. Gridnev、Yoshinori Yamanoi、Natsuka Higashi、Hideyuki Tsuruta、Masaya Yasutake、Tsuneo Imamoto

  DOI：10.1002/1615-4169(20010129)343:1<118::aid-adsc118>3.3.co;2-q

  日期：2001.1.29

  A new class of chiral C-2-symmetric bis(trialkyl)phosphine ligands has been prepared and used in Rh(I)-catalyzed asymmetric hydrogenation reactions. The Ligands, 1,2-bis(alkylmethylphosphino)ethanes 1 a-g (abbreviated as BisP*, alkyl = t-butyl, 1-adamantyl, 1-methylcyclohexyl, 1,1-diethylpropyl, cyclopentyl, cyclohexyl, isopropyl) and 1,2-bis(alkylmethylphosphino)methanes 2 a-d (abbreviated as MiniPHOS, alkyl = t-butyl, cyclohexyl, isopropyl, phenyl) are prepared by a simple synthetic approach based on the air-stable phosphine-boranes. These new ligands give the corresponding Rh(I) complexes, which are effective catalytic precursors for the asymmetric hydrogenation of a representative series of dehydroamino acids and itaconic acid derivatives. Enantioselectivities observed in these hydrogenations are universally high and in many cases exceed 99%. X-Ray characterization of four precatalysts, study of the pressure effects, deuteration experiments, and characterization of the wide series of intermediates in the catalytic cycle are used for the discussion of the possible correlation between the structure of the catalysts and the outcome of the catalytic asymmetric hydrogenation.
• Reaction of a Rhodium−MiniPHOS Complex with Dihydrogen:  NMR and Computational Study
  作者：Ilya D. Gridnev、Tsuneo Imamoto

  DOI：10.1021/om000304u

  日期：2001.2.1

  The rhodium-MiniPHOS complex [Rh((R,R)-(MeBuPCH2PMeBut)-P-t)(2)](+) BF4- (1) is reversibly and stereoselectively hydrogenated at low temperatures to give one isomer of cis-dihydride 2a. The second possible diastereomer, 2b, is not observed experimentally. DFT calculations suggest that 2b is 3.5 kcal mol(-1) less stable than 2a. The parameters of the equilibrium between 2a, 1, and H-2 determined by NMR are DeltaH = -7.7 +/- 0.1 kcal mol(-1) and DeltaS = -25 +/- 1 cal mol(-1) K-1. Formation of the trans-dihydride 3 is observed at around -20 degreesC. Most probably 3 is formed by isomerization of 2a or 2b. This isomerization involves reversible dissociation of the Rh-P bond. Similar dissociation of the Rh-P bond in 2a might make possible the substrate binding when 1 is used as a catalyst for asymmetric hydrogenation.
• AMIDASE AND USE THEREOF FOR PRODUCING 3-AMINOCARBOXYLIC ACID ESTERS
  申请人：Hauer Bernhard

  公开号：US20130005002A1

  公开（公告）日：2013-01-03

  Process for producing optically active 3-aminocarboxylic acid ester compounds of general Formula I, and the ammonium salts thereof, in which R 1 stands for alkyl, alkoxyalkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, or hetaryl, and R 2 stands for alkyl, cycloalkyl or aryl, in which an enantiomeric mixture of a simply N-acylated 3-aminocarboxylic acid ester of general formula (I.b), in which R 1 and R 2 have the meanings given above and R 3 stands for hydrogen, alkyl, cycloalkyl or aryl, is submitted to an enantioselective deacylation by adding a polypeptide according to claim 1.