(3S,4R)-dihydroxy-(2R)-(triphenylmethoxymethyl)tetrahydropyran | 171492-27-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: (3S,4R)-dihydroxy-(2R)-(triphenylmethoxymethyl)tetrahydropyran
• 英文别名: (2R,3S,4R)-2-(trityloxymethyl)oxane-3,4-diol
• CAS: 171492-27-6
• 化学式: C₂₅H₂₆O₄
• 分子量: 390.479
• InChiKey: OKCLJIGLDOWJIQ-SMIHKQSGSA-N

物化性质

• 沸点：
  552.4±50.0 °C(Predicted)
• 密度：
  1.208±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  氯二(3,5-二甲基苯基)膦 、 (3S,4R)-dihydroxy-(2R)-(triphenylmethoxymethyl)tetrahydropyran 在 吡啶 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 1,5-anhydro-2-deoxy-3,4-O-(bis(3,5-dimethylphenyl)phosphino)-6-O-(triphenylmetyl)-D-glucitol
  参考文献：
  名称：

  Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of R- or S-Amino Acids Using Natural Sugars as Ligand Precursors

  摘要：

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.

  DOI：

  10.1021/jo970884d
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 palladium on activated charcoal 甲醇 、 氢气 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 (3S,4R)-dihydroxy-(2R)-(triphenylmethoxymethyl)tetrahydropyran
  参考文献：
  名称：

  New homochiral cyclic diol ligands for titanium alkoxide catalyzed phosphonylation of aldehydes

  摘要：

  An investigation of the structural effects of chiral diol ligands on the enantioselectivity of phosphorylation was performed. Cyclic diols, and cyclohexanediol in particular, were identified as effective ligands for titanium alkoxide catalyzed asymmetric phosphorylation. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01139-3

文献信息

• [EN] CHIRAL CATALYSTS AND EPOXIDATION REACTIONS CATALYZED THEREBY<br/>[FR] CATALYSEUR CHIRAL ET REACTIONS D'EPOXYDATION CATALYSEES A L'AIDE DE CELUI-CI
  申请人：SMITHKLINE BEECHAM PLC

  公开号：WO1994003271A1

  公开（公告）日：1994-02-17

  (EN) A compound of formula (I), in which M is a transition metal ion; A is a counter-ion if required; r, s and t are independently 0 to 3 such that r+s+t is in the range of 1 to 3; Ra, Rb, Rc are each independently hydrogen or CH2OR' where R' is hydrogen or an organic group; B and E are independently oxygen, CH2, NRd in which Rd is alkyl, hydrogen, alkylcarbonyl, or arylcarbonyl or SOn where n is 0 or an integer 1 or 2, with the proviso that B and E are not simultaneously CH2 and that when B is oxygen, NRd or SOn, then r cannot be 0, and when E is oxygen, NRd or SOn, then t cannot be 0; R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are independently hydrogen, alkyl or alkoxy.(FR) L'invention concerne un composé représenté par la formule (I) dans laquelle M est un ion de métal transitoire; A représente un contre-ion si nécessaire; r, s, et t représentent indépendamment un entier de 0 à 3 de façon que r+s+t soit compris entre 1 et 3; Ra, Rb, Rc représentent indépendamment hydrogène ou CH2OR' où R' représente hydrogène ou un groupe organique; B et E représentent indépendamment oxygène, CH2, NRd où Rd représente alkyle, hydrogène, carbonyle d'alkyle ou carbonyle d'aryle ou SOn où n correspond à 0 ou à 1 ou 2, sous réserve que B et E ne représentent pas simultanément CH2 et que B représente oxygène, NRd ou SOn, r ne pouvant donc pas représenter 0, et lorsque E représente oxygène, NRd ou SOn, t ne peut représenter 0; R1, R2, R3, R4, R5, R6, R7, R8, R9 et R10 représentent indépendamment hydrogène, alkyle ou alcoxy.

  一种化合物的化学式(I)，其中M是过渡金属离子；A是必要时的对离子；r、s和t分别独立取0至3的整数，使得r+s+t在1至3的范围内；Ra、Rb、Rc各自独立取氢或CH2OR'，其中R'为氢或有机基团；B和E各自独立取氧、CH2、NRd，其中Rd为烷基、氢、烷基羰基或芳基羰基，或SOn，其中n为0或整数1或2，但B和E不能同时取CH2，且当B为氧、NRd或SOn时，r不能为0，当E为氧、NRd或SOn时，t不能为0；R1、R2、R3、R4、R5、R6、R7、R8、R9和R10各自独立取氢、烷基或烷氧基。
• PROCESS FOR EPOXIDISING PROCHIRAL OLEFINS
  申请人：SmithKline Beecham plc

  公开号：EP0741731B1

  公开（公告）日：2004-04-07
• CHIRAL CATALYSTS AND EPOXIDATION REACTIONS CATALYZED THEREBY
  申请人：SMITHKLINE BEECHAM PLC

  公开号：EP0655950B1

  公开（公告）日：1996-10-23
• PROCESS FOR EPOXIDISING PROCHIRAL OLEFINS AND A CATALYST THEREFOR AND INTERMEDIATES FOR MAKING THE CATALYST
  申请人：SMITHKLINE BEECHAM PLC

  公开号：EP0741731A1

  公开（公告）日：1996-11-13
• US5616750A
  申请人：——

  公开号：US5616750A

  公开（公告）日：1997-04-01