[[(4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl]di(R)-ethylidene]bis-[diphenylphosphine] | 258873-45-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [[(4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl]di(R)-ethylidene]bis-[diphenylphosphine]
• 英文别名: [[(4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl]di(R)-ethylidene]bis[diphenylphosphine]；3,4-O-isopropylidene-(3S,4S)-dihydroxy-(2R,5R)-bis(diphenylphosphino)hexane；(R,S,S,R)-DIOP*；[(1R)-1-[(4S,5S)-5-[(1R)-1-diphenylphosphanylethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]ethyl]-diphenylphosphane
• CAS: 258873-45-9
• 化学式: C₃₃H₃₆O₂P₂
• 分子量: 526.595
• InChiKey: XFIALTWJZRBKQY-QBQKZGEHSA-N

物化性质

• 沸点：
  603.0±30.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [[(4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl]di(R)-ethylidene]bis-[diphenylphosphine] 在 甲烷磺酸 、 水 作用下， 以 甲醇 为溶剂， 以85%的产率得到3,4-dihydroxy-2,5-bis(diphenylphosphanyl)hexane
  参考文献：
  名称：

  Development of DIOP derivatives as efficient ligands for asymmetric hydrogenation: factors controlling the reactivities and enantioselectivities

  摘要：

  Several DIOP derivatives have been developed as efficient ligands for Rh and Ir-catalyzed asymmetric hydrogenations. The conformational mobility of the backbone in this type of ligand plays an important role in governing both the reactivity and enantioselectivity. Isolation of pure pre-catalyst is another key factor to obtain high catalytic activity. (C) 2004 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetasy.2004.05.042
• 作为产物：
  描述：

  3,4-di-O-isopropylidene-D-mannitol 在 4-二甲氨基吡啶 、 lithium 、 三乙基硼氢化锂 、 potassium carbonate 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 反应 40.0h， 生成 [[(4S,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl]di(R)-ethylidene]bis-[diphenylphosphine]
  参考文献：
  名称：

  从碳水化合物中合成功能化磷烷的高度灵活的合成路线

  摘要：

  通过用磷化二锂试剂置换合适的二甲磺酸酯或环状硫酸酯，可以容易地从d-甘露醇制备高度官能化的膦烷15、17和26以及其中膦烷碳2和碳5的构型反转的相应非对映异构体。制备这些配体的二醇也可以转化为二芳基亚膦酸酯配体。还描述了产生带有半可溶性叔丁基硫基的相关单膦的途径。这些配体和相关脱保护衍生物的配合物可能可用于有机和水介质中的对映选择性催化。

  DOI：

  10.1021/jo991762j

文献信息

• Highly Flexible Synthetic Routes to Functionalized Phospholanes from Carbohydrates
  作者：Yuan-Yong Yan、T. V. RajanBabu

  DOI：10.1021/jo991762j

  日期：2000.2.1

  Highly functionalized phospholanes 15, 17, and 26 and the corresponding diastereomers in which the configurations of the phospholane carbon-2 and carbon-5 are inverted can be readily prepared from d-mannitol by displacement of the appropriate dimesylate or cyclic sulfate with dilithiumphosphide reagents. The diols from which these ligands are prepared can also be converted into diarylphosphinite ligands

  通过用磷化二锂试剂置换合适的二甲磺酸酯或环状硫酸酯，可以容易地从d-甘露醇制备高度官能化的膦烷15、17和26以及其中膦烷碳2和碳5的构型反转的相应非对映异构体。制备这些配体的二醇也可以转化为二芳基亚膦酸酯配体。还描述了产生带有半可溶性叔丁基硫基的相关单膦的途径。这些配体和相关脱保护衍生物的配合物可能可用于有机和水介质中的对映选择性催化。
• METHOD FOR SYNTHESIZING OPTICALLY ACTIVE CARBONYL COMPOUNDS
  申请人：BASF SE

  公开号：US20180057437A1

  公开（公告）日：2018-03-01

  The present invention relates to a process for the preparation of an optically active carbonyl compound by asymmetric hydrogenation of a prochiral α,β-unsaturated carbonyl compound with hydrogen in the presence of at least one optically active transition metal catalyst that is soluble in the reaction mixture and which has rhodium as catalytically active transition metal and a chiral, bidentate bisphosphine ligand, wherein the reaction mixture during the hydrogenation of the prochiral α,β-unsaturated carbonyl compound additionally comprises at least one compound of the general formula (I): in which R 1 , R 2 : are identical or different and are C 6 - to C 10 -aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino; Z is a group CHR 3 R 4 or aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C 1 - to C 6 -alkyl, C 3 - to C 6 -cycloalkyl, C 6 - to C 10 -aryl, C 1 - to C 6 -alkoxy and amino, wherein R 3 and R 4 are as defined in the claims and the description.

  本发明涉及一种通过在至少一种可溶于反应混合物中的光学活性过渡金属催化剂的存在下，将可溶性光学活性过渡金属铑和手性双膦配体作为催化活性过渡金属的α，β-不对称氢化的可半手性α，β-不饱和羰基化合物与氢气反应制备光学活性羰基化合物的方法。在氢化可半手性α，β-不饱和羰基化合物的过程中，反应混合物中还包括至少一种符合一般式（I）的化合物：其中 R1、R2：相同或不同，为未取代或带有一个或多个（例如1、2、3、4或5个）C6到C10芳基取代基的化合物，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基；Z是一种基团CHR3R4或未取代或带有一个或多个（例如1、2、3、4或5个）取代基的芳基，所述取代基选自C1到C6烷基、C3到C6环烷基、C6到C10芳基、C1到C6烷氧基和氨基，其中R3和R4如权利要求和说明书中定义。
• Method for the Production of Optically Active Carbonyl
  申请人：Jakel Christoph

  公开号：US20080269528A1

  公开（公告）日：2008-10-30

  The present invention relates to a process for preparing optically active carbonyl compounds by asymmetrically hydrogenating α,β-unsaturated carbonyl compounds in the presence of optically active transition metal catalysts which are soluble in the reaction mixture and have at least one carbon monoxide ligand. The present invention especially relates to a process for preparing optically active aldehydes or ketones, in particular citronellal, by asymmetrically hydrogenating the corresponding optically active α,β-unsaturated aldehydes or ketones.

  本发明涉及一种通过在存在可溶于反应混合物中并具有至少一个一氧化碳配体的光学活性过渡金属催化剂的情况下，对α，β-不饱和羰基化合物进行不对称氢化的方法。本发明特别涉及一种通过对相应的光学活性α，β-不饱和醛或酮进行不对称氢化而制备光学活性醛或酮的方法，特别是柠檬醛。
• METHOD FOR THE HOMOGENEOUS CATALYTIC REDUCTIVE AMINATION OF CARBONYL COMPOUNDS
  申请人：BASF SE

  公开号：US20180186725A1

  公开（公告）日：2018-07-05

  The present invention relates to a method for the reductive amination of a carbonyl compound, comprising one or more carbonyl groups amenable to reductive amination, forming the corresponding primary amine, characterized in that the reaction is carried out in the presence of a homogeneously dissolved catalyst complex K, comprising at least one metal atom from Group 8, 9 or 10 of the periodic table, bearing a bidentate phosphane ligand, a carbonyl ligand, a neutral ligand and a hydride ligand, and also an acid as co-catalyst.

  本发明涉及一种用于还原胺化羰基化合物的方法，包括一个或多个适宜进行还原胺化的羰基团，形成相应的一级胺，其特征在于在存在均匀溶解的催化剂复合物K的条件下进行反应，所述复合物K包括来自周期表第8、9或10族的至少一个金属原子，带有双膦配体、羰基配体、中性配体和氢化物配体，以及作为辅助催化剂的酸。
• Method for synthesizing optically active carbonyl compounds
  申请人：BASF SE

  公开号：US10301244B2

  公开（公告）日：2019-05-28

  The present invention relates to a process for the preparation of an optically active carbonyl compound by asymmetric hydrogenation of a prochiral α,β-unsaturated carbonyl compound with hydrogen in the presence of at least one optically active transition metal catalyst that is soluble in the reaction mixture and which has rhodium as catalytically active transition metal and a chiral, bidentate bisphosphine ligand, wherein the reaction mixture during the hydrogenation of the prochiral α,β-unsaturated carbonyl compound additionally comprises at least one compound of the general formula (I): in which R1, R2: are identical or different and are C6- to C10-aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C1- to C6-alkyl, C3- to C6-cycloalkyl, C6- to C10-aryl, C1- to C6-alkoxy and amino; Z is a group CHR3R4 or aryl which is unsubstituted or carries one or more, e.g. 1, 2, 3, 4 or 5, substituents which are selected from C1- to C6-alkyl, C3- to C6-cycloalkyl, C6- to C10-aryl, C1- to C6-alkoxy and amino, wherein R3 and R4 are as defined in the claims and the description.

  本发明涉及一种光学活性羰基化合物的制备工艺，该工艺是在至少一种光学活性过渡金属催化剂（可溶于反应混合物中）的存在下，以铑作为催化活性过渡金属和手性双叉双膦配体，通过氢气对亲手性α，β-不饱和羰基化合物进行不对称氢化，其中亲手性α，β-不饱和羰基化合物氢化过程中的反应混合物包括至少一种光学活性过渡金属催化剂（可溶于反应混合物中）和一种手性双叉双膦配体、其中手性 α，β-不饱和羰基化合物氢化过程中的反应混合物还包括至少一种通式 (I) 的化合物： 其中 R1、R2：相同或不同，是未被取代的 C6 至 C10 芳基，或带有一个或多个（如 1、2、3、4 或 5 个）选自 C1 至 C6 烷基、C3 至 C6 环烷基、C6 至 C10 芳基、C1 至 C6 烷氧基和氨基的取代基； Z 是未被取代的基团 CHR3R4 或芳基，或带有一个或多个（如 1、2、3、4 或 5 个）选自 C1 至 C6 烷基、C3 至 C6 环烷基、C6 至 C10 芳基、C1 至 C6 烷氧基和氨基的取代基，其中 R3 和 R4 如权利要求和说明中所定义。