(-)-N-((S)-α-methylbenzyl)dichlorothiophosphoroamidate | 147864-29-7

• 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: (-)-N-((S)-α-methylbenzyl)dichlorothiophosphoroamidate
• 英文别名: (1S)-N-dichlorophosphinothioyl-1-phenylethanamine
• CAS: 147864-29-7
• 化学式: C₈H₁₀Cl₂NPS
• 分子量: 254.12
• InChiKey: HCGSGSANCKVTBD-ZETCQYMHSA-N

物化性质

• 沸点：
  325.6±35.0 °C(Predicted)
• 密度：
  1.361±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  44.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-N-((S)-α-methylbenzyl)dichlorothiophosphoroamidate 在 吡啶 、 四丁基氢氧化铵 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 (1,11-Dimethoxy-6-thioxo-5,7-dioxa-6λ⁵-phospha-dibenzo[a,c]cyclohepten-6-yl)-methyl-((S)-1-phenyl-ethyl)-amine
  参考文献：
  名称：

  Two new efficient preparations of enantiopure 2,2′-dihydroxy-6,6′-dimethoxy-1,1′-biphenyl

  摘要：

  Two new useful methods for the preparation of diol 1 starting from available compounds are described. Separation of the two enantiomers entails resolution of racemic diol 1 via the corresponding diastereomeric N-methylated phosphorothioamidates. Their separation by recrystallization followed by reduction afforded diol (aS)-1 and (aR)-1 in 100% and 72% ee, respectively. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00021-9
• 作为产物：
  描述：

  (S)-(-)- α-甲基苄胺 在 吡啶 、 三氯硫磷 作用下， 以97%的产率得到(-)-N-((S)-α-methylbenzyl)dichlorothiophosphoroamidate
  参考文献：
  名称：

  Preparation of enantiomerically pure 1,1'-binaphthalene-2,2'-diol and 1,1'-binaphthalene-2,2'-dithiol

  摘要：

  A practical preparation of enantiomerically pure 1,1'-binaphthalene-2,2'-diol (1) and 1,1'-binaphthalene-2,2'-dithiol (2) is reported. Enantiopure 2 is obtained from enantiopure 1 via Newman-Kwart rearrangement of the thiocarbamoyl derivative 5 under controlled reaction conditions. The enantiopure starting diol 1 was obtained by a simple and inexpensive method engaging condensation of thiophosphoryl chloride and (S)-(-)-alpha-methylbenzylamine in pyridine and reaction of the resulting phosphoramidate a with racemic binaphthol 1 to give quantitatively a 1:1 mixture of diastereoisomers 4 that were cleanly separated by a single recrystallization from a chloroform-ethanol mixture in very high yield. The procedures can be scaled up easily.

  DOI：

  10.1021/jo00059a025

文献信息

• Enantiopure 2,2′-dihydroxy-3,3′-dimethoxy-5,5′-diallyl-6,6′-dibromo-1,1′-biphenyl: a conformationally stable C2-dimer of a eugenol derivative
  作者：Giovanna Delogu、Davide Fabbri、Maria Antonietta Dettori、Alessandra Forni、Gianluigi Casalone

  DOI：10.1016/j.tetasy.2003.11.020

  日期：2004.1

  The preparation and resolution of the title conformationally stable biphenyl 9 has been performed in high chemical yield starting from eugenol 1. Enantiopure biphenyls (aR)-(+)-9 and (aS)-(−)-9 were achieved, respectively, by resolution of the corresponding menthylcarbonate diastereomer and subsequent reduction. Absolute configuration and specific rotation were correlated by X-ray analysis of the crystal

  从丁子香酚1开始，以高化学收率进行了标题构象稳定的联苯9的制备和拆分。通过拆分相应的碳酸薄荷酯非对映异构体并随后还原，分别获得了对映纯联苯（a R）-（+）- 9和（a S）-（-）- 9。通过X射线分析非对映纯硫代磷酸氨基硫代磷酸酯（R，S）-（-）- 16的晶体结构，将绝对构型和比旋光相关联。
• C2-Symmetric sulfur derivatives of 2,2′,3,3′-tetramethoxybiphenyl
  作者：Giovanna Delogu、Davide Fabbri、Maria Antonietta Dettori、Alessandra Forni、Gianluigi Casalone

  DOI：10.1016/s0957-4166(01)00247-6

  日期：2001.6

  A practical route to prepare dithioether, thiophene and thiophene S-dioxide derivatives of 2.2 ' ,3,3 ' -tetramethoxy-1,1 ' -biphenyl 1 is described. Resolution of 6,6 ' -bis(methylithio)-3.3 ' -dimethoxy-[1,1 ' -biphenyl]-2.2 ' -diol 15 was achieved and its absolute configuration was assigned by X-ray analysis of the corresponding phosphorothioamidate diastereomer 18. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Preparation of enantiomerically pure 1,1'-binaphthalene-2,2'-diol and 1,1'-binaphthalene-2,2'-dithiol
  作者：Davide Fabbri、Giovanna Delogu、Ottorino De Lucchi

  DOI：10.1021/jo00059a025

  日期：1993.3

  A practical preparation of enantiomerically pure 1,1'-binaphthalene-2,2'-diol (1) and 1,1'-binaphthalene-2,2'-dithiol (2) is reported. Enantiopure 2 is obtained from enantiopure 1 via Newman-Kwart rearrangement of the thiocarbamoyl derivative 5 under controlled reaction conditions. The enantiopure starting diol 1 was obtained by a simple and inexpensive method engaging condensation of thiophosphoryl chloride and (S)-(-)-alpha-methylbenzylamine in pyridine and reaction of the resulting phosphoramidate a with racemic binaphthol 1 to give quantitatively a 1:1 mixture of diastereoisomers 4 that were cleanly separated by a single recrystallization from a chloroform-ethanol mixture in very high yield. The procedures can be scaled up easily.
• Chiral nonracemic C2-symmetry biphenyls by desymmetrization of 6,6′,2,2′-tetramethoxy-1,1′-biphenyl
  作者：Giovanna Delogu、Davide Fabbri、Maria Antonietta Dettori、Alessandra Forni、Gianluigi Casalone

  DOI：10.1016/s0957-4166(00)00410-9

  日期：2000.11

  Regioselective bromination of the title biphenyl 1 at the 3 and 3' positions and simultaneous desymmetrization of the biphenyl has been achieved. Metal-halide exchange at the 3,3' positions facilitated the introduction of functional groups in good yield. Regioselective reduction was obtained by using (CH3)(3)SiI, L-Selectride and HI according to the functional groups on the biphenyls. Resolution of 6,6',2,2'-tetramethoxy-3,3'-dimethyl-1,1'-biphenyl 3 was achieved by its conversion to the corresponding phosphorothioamidate diastereomers of the (S)-(-)-alpha -methylbenzylamine. The absolute configuration of (M)-(+)-3 was confirmed by X-ray analysis of the corresponding diastereomer. (C) 2000 Elsevier Science Ltd. All rights reserved.
• New axially chiral sulfur compounds: Synthesis and conformational stability of enantiopure 4,4′-biphenanthrene-3,3′-dithiol and related atropisomeric derivatives
  作者：Antonio Dore、Davide Fabbri、Serafino Gladiali、Giovanni Valle

  DOI：10.1016/0957-4166(95)00074-y

  日期：1995.3

  Enantiopure (R)- and (S)-4,4'-biphenanthrene-3,3'-dithiol la has been prepared for the first time through a synthetic procedure involving in the key step a stereoconservative Newman-Kwart thermorearrangement of the bis-N,N-dimethylthiocarbamoyl ester of(R)- and (S)-biphenanthrol 2b, respectively. The atropisomeric conformations of la are not interconverted even at temperatures as high as 285 degrees C, whereas the related biphenanthrothiophene 3 is completely racemized in a few minutes at 250 degrees C. The axially chiral backbone of la has been incorporated in a set of novel C-2 symmetry sulfur reagents suitable for a variety of stereoselective reactions.