(R)-(-)-2-(N-piperidyl)-2'-(diphenylphosphino)-1,1'-binaphthyl

• 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)-(-)-2-(N-piperidyl)-2'-(diphenylphosphino)-1,1'-binaphthyl
• 英文别名: Diphenyl-[1-(2-piperidin-1-ylnaphthalen-1-yl)naphthalen-2-yl]phosphane
• 化学式: C₃₇H₃₂NP
• 分子量: 521.642
• InChiKey: XSGYWGOIHJCZIE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  39
• 可旋转键数：
  5
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (R)-(+)-N-(2'-hydroxy-[1,1']binaphthalenyl-2-yl)acetamide 在 吡啶 、 palladium diacetate 、 sodium tetrahydroborate 、 硫酸 、 三氯硅烷 、 三乙胺 、 N,N-二异丙基乙胺 、 1,4-双(二苯基膦)丁烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 、 xylene 为溶剂， 反应 12.25h， 生成 (R)-(-)-2-(N-piperidyl)-2'-(diphenylphosphino)-1,1'-binaphthyl
  参考文献：
  名称：

  Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution

  摘要：

  (R)-(+)-2-Amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 5) can be readily converted into a series of novel N,N-disubstituted aminophosphines 9 and 23-25. The N,N-dimethyl derivative (R)-9 (MAP) was prepared via a sequence involving reductive alkylation with CH2O and NaBH4 (5 --> 6), Pd-(O)-catalyzed coupling of the corresponding triflate with Ph2P(O)H (7 --> 8), and reduction of the resulting phosphine oxide with Cl3SiH (8 --> 9). Variation of this scheme was required for the preparation of 23-25 as the phosphinylation failed in the presence of bulky N substituents; the N-protected triflate 17 was first coupled with Ph2P(O)H, and the resulting phosphine oxide 18 was reduced with Cl3SiH to give the aminophosphine 19, which was then subjected to reductive alkylation with individual ketones and NaBH4. The new P,N-binaphthyls thus obtained (23-25 and 9) were utilized as chiral ligands in Pd(O)-catalyzed allylic substitution. The enantioselectivites obtained for racemic 1,3-diphenylprop-2-en-1-yl acetate (+/-)-26 and malonate nucleophiles, which gave (S)-(-28, (R)-(+)-29, and (R)-(+)-30 as the respective products tin up to 71-73% ee at room temperature with Cs2CO3 in CH2Cl2 and 9 or 23 as a ligand), are interpreted in terms of the chelated transition state 37 and preferential attack at the allylic terminus that is trans with respect to the phosphorus acceptor atom.

  DOI：

  10.1021/jo980757x

文献信息

• Derivatives of 2-Amino-2‘-diphenylphosphino-1,1‘-binaphthyl (MAP) and Their Application in Asymmetric Palladium(0)-Catalyzed Allylic Substitution
  作者：Štěpán Vyskočil、Martin Smrčina、Vladimír Hanuš、Miroslav Polášek、Pavel Kočovský

  DOI：10.1021/jo980757x

  日期：1998.10.1

  (R)-(+)-2-Amino-2'-hydroxy-1,1'-binaphthyl (NOBIN, 5) can be readily converted into a series of novel N,N-disubstituted aminophosphines 9 and 23-25. The N,N-dimethyl derivative (R)-9 (MAP) was prepared via a sequence involving reductive alkylation with CH2O and NaBH4 (5 --> 6), Pd-(O)-catalyzed coupling of the corresponding triflate with Ph2P(O)H (7 --> 8), and reduction of the resulting phosphine oxide with Cl3SiH (8 --> 9). Variation of this scheme was required for the preparation of 23-25 as the phosphinylation failed in the presence of bulky N substituents; the N-protected triflate 17 was first coupled with Ph2P(O)H, and the resulting phosphine oxide 18 was reduced with Cl3SiH to give the aminophosphine 19, which was then subjected to reductive alkylation with individual ketones and NaBH4. The new P,N-binaphthyls thus obtained (23-25 and 9) were utilized as chiral ligands in Pd(O)-catalyzed allylic substitution. The enantioselectivites obtained for racemic 1,3-diphenylprop-2-en-1-yl acetate (+/-)-26 and malonate nucleophiles, which gave (S)-(-28, (R)-(+)-29, and (R)-(+)-30 as the respective products tin up to 71-73% ee at room temperature with Cs2CO3 in CH2Cl2 and 9 or 23 as a ligand), are interpreted in terms of the chelated transition state 37 and preferential attack at the allylic terminus that is trans with respect to the phosphorus acceptor atom.