1,4-bis(diphenylphosphino)-2,3-butanediol

• 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: 1,4-bis(diphenylphosphino)-2,3-butanediol
• 英文别名: (2r,3r)-2,3-Dihydroxy-1,4-bis(diphenylphosphino)butane；(2R,3R)-1,4-bis(diphenylphosphanyl)butane-2,3-diol
• 化学式: C₂₈H₂₈O₂P₂
• 分子量: 458.477
• InChiKey: AOHZKGPNHXMRGN-NSOVKSMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-naphthyloxydichlorophosphine 、 1,4-bis(diphenylphosphino)-2,3-butanediol 在 三乙胺 作用下， 以 乙醚 为溶剂， 以45.5%的产率得到(4R,5R)-4,5-bis(diphenylphosphinomethyl)-2-(α-naphthoxy)-1,3,2-dioxaphospholane
  参考文献：
  名称：

  Analogues of DIOP. Synthesis, reactivity, and NMR behaviour

  摘要：

  The (4R,5R)-4,5-Bis(diphenylphosphinomethyl)-2-(alpha-naphthoxy)-1,3,2-dioxaphospholane (1) and (4R,5R)-4,5-bis(diphenylphosphinomethyl)-2-dimethylamino-2-oxo-1,3,2-dioxaphospholane (2), analogues of the chiral bisphosphine ligand DIOP, have been synthesized. Both compounds have a second phosphorus functionality in the backbone of the chiral bisphosphine. That the reactivities of the various phosphorus atoms in 1 are different was shown for the reaction with BH3. The complexation behaviour of 1 towards Rh(I) was studied with the aid of P-31 NMR spectroscopy.

  DOI：

  10.1016/0022-328x(94)80172-x
• 作为产物：
  描述：

  异丙烯基-2,3-二羟基-1,4-双二苯基膦丁烷 在 高氯酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以70%的产率得到1,4-bis(diphenylphosphino)-2,3-butanediol
  参考文献：
  名称：

  二膦配体的铑（I）配合物催化丙烯酸的不对称转移加氢

  摘要：

  已经研究了许多手性的1,2,1,3和1,4-二膦作为铑催化的从甲酸及其盐到丙烯酸底物的氢转移的配体。结果表明，催化体系的活性和选择性强烈依赖于螯合环的大小和配体的刚性，反应介质以及底物的性质。

  DOI：

  10.1016/s0022-328x(97)00628-1
• 作为试剂：
  描述：

  1-辛炔 、 苯甲酸 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 1,4-bis(diphenylphosphino)-2,3-butanediol 、 caesium carbonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 生成 苯甲酸1-己基乙烯基酯 、 (S)-1-octen-3-yl benzoate
  参考文献：
  名称：

  Enantioselective Redox-Neutral Rh-Catalyzed Coupling of Terminal Alkynes with Carboxylic Acids Toward Branched Allylic Esters

  摘要：

  We report on the first enantioselective variant of the atom-economic and redox-neutral coupling of carboxylic acids with terminal alkynes under rhodium catalysis utilizing the chiral, bidentate (R,R)-Cp-DIOP ligand. This represents the first example of this convenient asymmetric access to valuable branched allylic esters. The utility of this methodology is demonstrated by both a reaction performed on large scale and a short three-step synthesis of two naturally occurring gamma-butyrolactones. A stereochemical model explaining the observed absolute configuration of the products based on DFT calculations is given.

  DOI：

  10.1021/jacs.5b01131

文献信息

• Decarboxylative Aldol Reactions of Allyl β-Keto Esters via Heterobimetallic Catalysis
  作者：Sha Lou、John A. Westbrook、Scott E. Schaus

  DOI：10.1021/ja045981k

  日期：2004.9.1

  Mild and selective heterobimetallic-catalyzed decarboxylative aldol reactions involving allyl beta-keto esters have been developed. The reaction is promoted by Pd(0)- and Yb(III)-DIOP complexes at room temperature and involves the in situ formation of a ketone enolate from allyl beta-keto esters followed by addition of the enolate to aldehydes. The reaction is a new example of heterobimetallic catalysis

  涉及烯丙基β-酮酯的温和且选择性的杂双金属催化的脱羧醛醇反应已被开发。该反应在室温下由 Pd(0)-和 Yb(III)-DIOP 配合物促进，包括由烯丙基 β-酮酯原位形成酮烯醇化物，然后将烯醇化物加入醛。该反应是异双金属催化的一个新例子，其中优化的反应条件需要添加两种金属。
• A new approach to the synthesis of (−)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane(diop)
  作者：San-qi Zhang、Sheng-yong Zhang、Rui Feng

  DOI：10.1016/s0957-4166(00)82351-4

  日期：1991.1

  (-)-2,3-O-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP) has been prepared by reaction of (-)-1,2:3,4-diepoxybutane with lithium diphenylphosphide followed by ketalisation with 2,2-dimethoxypropane.

  (-)-2,3-O-异丙叉基-2,3-二羟基-1,4-双(二苯基磷)丁烷（DIOP）是通过(-)-1,2:3,4-二环氧丁烷与二苯基磷化锂反应，随后与2,2-二甲氧基丙烷进行缩酮化反应制备而成。
• New Chiral Diphosphines, 2,3-Bis(siloxy)-1,4-bis(diphenylphosphino)butanes, and Their Cationic Rh(I) Complexes: Synthesis and Structures
  作者：Kohei Tamao、Kazunori Nakamura、Shigehiro Yamaguchi、Motoo Shiro、Seiki Saito

  DOI：10.1246/cl.1996.1007

  日期：1996.11

  A series of 2,3-bis(siloxy)-1,4-bis(diphenylphosphino)butanes SILOPs, possessing various siloxy groups, and their Rh(I) complexes have been prepared. The X-ray structure of a SILOP shows a staggered conformation with two siloxy groups in the anti positions. The X-ray crystal structure of a cationic Rh(I)-SILOP complex, however, shows an anti arrangement of not the two siloxy groups but the two silyl

  已经制备了一系列具有各种甲硅烷氧基的 2,3-双(甲硅烷氧基)-1,4-双(二苯基膦基)丁烷 SILOPs 及其 Rh(I) 配合物。SILOP 的 X 射线结构显示出在反位具有两个甲硅烷氧基的交错构象。然而，阳离子 Rh(I)-SILOP 复合物的 X 射线晶体结构显示出不是两个甲硅烷氧基而是两个甲硅烷基相对于 O-O 轴的反排列，这加强了 C2 对称环境围绕金属中心。
• A novel method for the synthesis of chiral sulfonated phosphines
  作者：Stephan Trinkhaus、Jens Holz、Rüdiger Selke、Armin Börner

  DOI：10.1016/s0040-4039(96)02407-0

  日期：1997.2

  The selective and smooth introduction of sulfonate groups in chiral diphosphines by the reaction of hydroxy diphosphines with o-sulfobenzoic anhydride in the presence of Na2CO3 or n-butyl lithium, respectively, is described.

  分别描述了在Na 2 CO 3或正丁基锂存在下，通过羟基二膦与邻磺基苯甲酸酐的反应，选择性和平稳地将磺酸酯基引入手性二膦中。
• A boron analog of diop: synthesis and properties
  作者：A. Börner、J. Ward、K. Kortus、H.B. Kagan

  DOI：10.1016/s0957-4166(00)80072-5

  日期：1993.10

  A rhodium complex of a boron analog of DIOP, which is a model for a tailored bimetallic catalyst possessing dual functions, is an active catalyst for hydrogenation and hydrosilylation.