(R,R)-Taddol phosphorochloridite | 945668-51-9

• 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: (R,R)-Taddol phosphorochloridite
• 英文别名: (S,S)-2,2-dimethyl-α,α,α',α'-tetraphenyldioxolane-4,5-dimethanol phosphorochloridite；(3aS,8aS)-6-chloro-2,2-dimethyl-4,4,8,8-tetraphenyltetrahydro[1,3]dioxolo[4,5-e][1,3,2]dioxaphosphepine；(S,S)-TADDOL phosphorochloridite；(R,R)-Taddol-PCl
• CAS: 945668-51-9
• 化学式: C₃₁H₂₈ClO₄P
• 分子量: 530.988
• InChiKey: QRXSVIOOMCPHRU-NSOVKSMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.91
• 重原子数：
  37.0
• 可旋转键数：
  4.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (R,R)-Taddol phosphorochloridite 在 水 、 三乙胺 作用下， 生成 (1R,7R)-9,9-dimethyl-4-hydrido-4-oxo-2,2,6,6-tetraphenyl-3,5,8,10-tetraoxa-4-phosphabicyclo[5.3.0]decane
  参考文献：
  名称：

  Ni–Al Bimetallic Catalyzed Enantioselective Cycloaddition of Cyclopropyl Carboxamide with Alkyne

  摘要：

  A Ni-Al bimetallic catalyzed enantioselective cycloaddition reaction of cyclopropyl carboxamides with alkynes has been developed. A series of cyclopentenyl carboxamides were obtained in up to 99% yield and 94% ee. The bifunctional-ligand-enabled bimetallic catalysis proved to be an, efficient strategy for the C-C bond cleavage of unreactive cyclopropanes.

  DOI：

  10.1021/jacs.7b09947
• 作为产物：
  描述：

  溴苯 在 碘 、 magnesium 、 三乙胺 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 生成 (R,R)-Taddol phosphorochloridite
  参考文献：
  名称：

  Ni–Al Bimetallic Catalyzed Enantioselective Cycloaddition of Cyclopropyl Carboxamide with Alkyne

  摘要：

  A Ni-Al bimetallic catalyzed enantioselective cycloaddition reaction of cyclopropyl carboxamides with alkynes has been developed. A series of cyclopentenyl carboxamides were obtained in up to 99% yield and 94% ee. The bifunctional-ligand-enabled bimetallic catalysis proved to be an, efficient strategy for the C-C bond cleavage of unreactive cyclopropanes.

  DOI：

  10.1021/jacs.7b09947

文献信息

• Enantioselective Synthesis of [6]Carbohelicenes
  作者：Elisa González-Fernández、Leo D. M. Nicholls、Lukas D. Schaaf、Christophe Farès、Christian W. Lehmann、Manuel Alcarazo

  DOI：10.1021/jacs.6b12443

  日期：2017.2.1

  The use of α-cationic phosphonites derived from TADDOL as ancillary ligands has allowed a highly regio- and enantioselective synthesis of substituted [6]carbohelicenes by sequential Au-catalyzed intramolecular hydroarylation of diynes. Key for these results is the modular structure of these new ligands, and the enhanced reactivity that they impart to Au(I)-centers after coordination.

  使用衍生自 TADDOL 的 α-阳离子亚膦酸酯作为辅助配体，允许通过连续 Au 催化的二炔分子内加氢芳基化来高度区域和对映选择性合成取代的 [6] 碳螺旋。这些结果的关键是这些新配体的模块化结构，以及它们在配位后赋予 Au(I) 中心增强的反应性。
• Ni-Catalyzed Asymmetric Cycloisomerization of Dienes by Using TADDOL Phosphoramidites
  作者：Christian Schmitz、Walter Leitner、Giancarlo Franciò

  DOI：10.1002/chem.201500352

  日期：2015.7.20

  3‐dioxolane‐4,5‐dimethanol (TADDOL)‐based phosphoramidites has been synthesized and applied in the Ni‐catalyzed cycloisomerization of different dienes. Through the systematic variation of the three structural motifs of the lead structure, that is, the amine moiety, the protecting group, and the aryl substituents, the ligand features could be optimized for the asymmetric cycloisomerization of the model substrate

  合成了基于α，α，α，α-四芳基-1,3-二氧戊环-4,5-二甲醇（TADDOL）的亚磷酰胺库，并将其用于Ni催化的不同二烯的环异构化。通过铅结构的三个结构基序（即胺部分，保护基和芳基取代基）的系统变化，可以优化配体特征，以使模型底物二烯丙基丙二酸二乙酯的不对称环异构化。新催化体系的底物范围已扩展到其他二烯丙基底物，包括不对称二烯。总体上具有高达13 500 h -1的极高活性，对五元外亚甲基亚环戊烷的选择性很高，对映选择性高达92％  ee 已经实现。
• Rhodium-Catalyzed Asymmetric Hydroformylation with Taddol-Based IndolPhos Ligands
  作者：Jeroen Wassenaar、Bas de Bruin、Joost N. H. Reek

  DOI：10.1021/om100236v

  日期：2010.6.28

  their use in asymmetric hydroformylation (AHF) reactions are reported. Moderate to good enantioselectivities are obtained for styrene, vinyl acetate, and allyl cyanide up to 72%, 74%, and 63% ee, respectively. High b/l ratios are obtained, which results in a high net yield of the desired chiral aldehyde. An unprecedented temperature-dependent reversal of enantioselectivity is found when using ligands

  据报道，一个基于Taddol的IndolPhos配体2a - g的小型文库及其在不对称加氢甲酰化（AHF）反应中的用途。对于苯乙烯，乙酸乙烯酯和烯丙基氰化物，分别获得了高达72％，74％和63％ee的中等至良好的对映选择性。获得高的b / l比，这导致所需手性醛的高净产率。当使用配体2d，e时，发现空前的温度依赖性对映选择性逆转，该配体基于二甲苯基衍生的Taddol在苯乙烯的Rh催化AHF中。此外，与其他所有基于（R，R）-酒石酸。配体2a和2d显示出相似的动力学曲线，最好用I型动力学来描述。氘代甲酰化实验表明，在所应用的条件下，将烯烃插入Rh-H键是不可逆的。高压NMR研究表明，氢化双羰基铑物种是催化剂的静止状态，其特征在于配体的赤道-顶配位，在顶位优选膦（异构体A）。然而，在配体2d的情况下，亚磷酰胺占据顶端位置B的异构体的自由能仅比异构体A略高。提议通过配体2d，e的异构体B和所有其
• Asymmetric Hydrogenation of Seven-Membered C=N-containing Heterocycles and Rationalization of the Enantioselectivity
  作者：Bugga Balakrishna、Antonio Bauzá、Antonio Frontera、Anton Vidal-Ferran

  DOI：10.1002/chem.201601464

  日期：2016.7.18

  catalyze the enantioselective hydrogenation of diverse seven‐membered C=N‐containing heterocyclic compounds (eleven examples; up to 97 % ee). The P‐OP ligand L3, which incorporates an ortho‐diphenyl substituted octahydrobinol phosphite fragment, provided the highest enantioselectivities in the hydrogenation of most of the heterocyclic compounds studied. The observed stereoselection was rationalized by means

  具有膦-亚磷酸酯配体的铱（I）络合物可有效催化多种七元含C = N杂环化合物的对映选择性氢化（11个例子；ee高达97％）。P-OP配体L3结合有邻-二苯基取代的八氢联苯酚亚磷酸酯片段，在大多数所研究的杂环化合物的氢化过程中提供了最高的对映选择性。观察到的立体选择通过DFT计算得以合理化。
• Chiral Calix[4]arene‐Based Diphosphites as Ligands in the Asymmetric Hydrogenation of Prochiral Olefins
  作者：Angelica Marson、Zoraida Freixa、Paul C. J. Kamer、Piet W. N. M. van Leeuwen

  DOI：10.1002/ejic.200700764

  日期：2007.10

  Chiral calixarene-based diphosphite ligands 3a–d have been obtained via lower-rim functionalisation of the p-tert-butylcalix[4]arene core. High enantiomeric excesses (up to 94 %) and good activities were obtained in the rhodium-catalyzed asymmetric hydrogenation of prochiral olefins withTADDOL-containing diphosphites 3c,d. This is the firstexample of chiral calix[4]arene-modified ligands that induce

  手性杯芳烃基二亚磷酸酯配体 3a-d 是通过对叔丁基杯 [4] 芳烃核的下缘官能化获得的。在铑催化的前手性烯烃与含 TADDOL 的二亚磷酸酯 3c、d 的不对称氢化中获得了高对映体过量（高达 94%）和良好的活性。这是手性杯 [4] 芳烃修饰配体的第一个例子，可在金属催化的不对称反应中诱导高对映选择性。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)