2-(1-phenylethoxy)-4-methyl-1,3,2-dioxaphosphorinane

• 分子结构分类: 有机化合物 - 有机磷化合物 - 亚磷酸三烷基酯
• 英文名称: 2-(1-phenylethoxy)-4-methyl-1,3,2-dioxaphosphorinane
• 英文别名: (2R,4R)-4-methyl-2-[(1R)-1-phenylethoxy]-1,3,2-dioxaphosphinane
• 化学式: C₁₂H₁₇O₃P
• 分子量: 240.239
• InChiKey: JUHSPNQRPDDSJP-GLKRBJQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (R)-(-)-1,3-丁二醇 、 (R)-(+)-1-苯基乙醇 、 六乙基亚磷酸胺 在 四氮唑 、 对甲苯磺酸 作用下， 生成 2-(1-phenylethoxy)-4-methyl-1,3,2-dioxaphosphorinane 、 2-(1-phenylethoxy)-4-methyl-1,3,2-dioxaphosphorinane
  参考文献：
  名称：

  Photo-Arbuzov Rearrangements of Benzylic Phosphites. Stereochemistry at Migratory Carbon

  摘要：

  The stereochemistry of the photo-Arbuzov rearrangement of the benzylic phosphite trans-(R,R')-10 to the corresponding phosphonate, 11, has been determined by P-31 NMR spectroscopy and X-ray crystallography. The reaction is shown to occur with predominant retention of configuration at the stereogenic migratory carbon center of configuration R' in starting trans-(R,R')-10 and the predominant product cis-(R,R')-11. Thus, reaction of optically active phosphoramidite 13 (R/S ratio 98/2, 96% ee) with 1-phenylethanol of high optical purity (R'/S' ratio, 97/3, 94% ee) gives phosphite trans-10 (cis/trans ratio, 97/3) almost entirely as the single enantiomer, trans-(R,R')-10. Irradiation of trans-(R,R')-10 in acetonitrile with 254 nm ultraviolet light converted it cleanly to two diastereomers of phosphonate cis-11 in 80/20 ratio (P-31 NMR). The major (80%) isomer was isolated, recrystallized, and shown by X-ray crystallography to be cis-(R,R')-11. The lesser (20%) product is identified, on the basis of its 31P NMR chemical shift, as the diastereomer cis-(R,S')-11. (Assignments derived from photorearrangement of totally racemic cis-10 prepared from reaction of racemic 1-phenylethanol with racemic 13.) The generation of trans-(R,S')-11 is attributed to the formation (Scheme 1) from trans-(R,R')-10 of short-lived, predominantly singlet, free radical pairs (12a) that largely (similar or equal to 80%) undergo combination to form cis-(R,R')-11. To a lesser extent (similar or equal to 20%), the 1-phenylethyl radicals (C) of the pair 12a are converted by rotation to C' to generate the stereochemically distinct radical pair 12b that then combines to form cis-(R,S')-11. To a first approximation, combination (k(comb)) is four times as fast as rotation (k(rot)). During the photorearrangement the trans/cis ratios of starting phosphite 10 and product phosphonate 11 are unchanged as is consistent with the generation of phosphinoyl radical E that is configurationally stable at phosphorus.

  DOI：

  10.1021/jo9807969

文献信息

• Photo-Arbuzov Rearrangements of Benzylic Phosphites. Stereochemistry at Migratory Carbon
  作者：Worawan Bhanthumnavin、Atta Arif、Wesley G. Bentrude

  DOI：10.1021/jo9807969

  日期：1998.10.1

  The stereochemistry of the photo-Arbuzov rearrangement of the benzylic phosphite trans-(R,R')-10 to the corresponding phosphonate, 11, has been determined by P-31 NMR spectroscopy and X-ray crystallography. The reaction is shown to occur with predominant retention of configuration at the stereogenic migratory carbon center of configuration R' in starting trans-(R,R')-10 and the predominant product cis-(R,R')-11. Thus, reaction of optically active phosphoramidite 13 (R/S ratio 98/2, 96% ee) with 1-phenylethanol of high optical purity (R'/S' ratio, 97/3, 94% ee) gives phosphite trans-10 (cis/trans ratio, 97/3) almost entirely as the single enantiomer, trans-(R,R')-10. Irradiation of trans-(R,R')-10 in acetonitrile with 254 nm ultraviolet light converted it cleanly to two diastereomers of phosphonate cis-11 in 80/20 ratio (P-31 NMR). The major (80%) isomer was isolated, recrystallized, and shown by X-ray crystallography to be cis-(R,R')-11. The lesser (20%) product is identified, on the basis of its 31P NMR chemical shift, as the diastereomer cis-(R,S')-11. (Assignments derived from photorearrangement of totally racemic cis-10 prepared from reaction of racemic 1-phenylethanol with racemic 13.) The generation of trans-(R,S')-11 is attributed to the formation (Scheme 1) from trans-(R,R')-10 of short-lived, predominantly singlet, free radical pairs (12a) that largely (similar or equal to 80%) undergo combination to form cis-(R,R')-11. To a lesser extent (similar or equal to 20%), the 1-phenylethyl radicals (C) of the pair 12a are converted by rotation to C' to generate the stereochemically distinct radical pair 12b that then combines to form cis-(R,S')-11. To a first approximation, combination (k(comb)) is four times as fast as rotation (k(rot)). During the photorearrangement the trans/cis ratios of starting phosphite 10 and product phosphonate 11 are unchanged as is consistent with the generation of phosphinoyl radical E that is configurationally stable at phosphorus.