(S)-2-(Benzhydrylidene-amino)-3-methoxycarbonyl-succinic acid 1-tert-butyl ester 4-methyl ester | 176965-33-6

• 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: (S)-2-(Benzhydrylidene-amino)-3-methoxycarbonyl-succinic acid 1-tert-butyl ester 4-methyl ester
• 英文别名: 2-O-tert-butyl 1-O,1-O-dimethyl (2S)-2-(benzhydrylideneamino)ethane-1,1,2-tricarboxylate
• CAS: 176965-33-6
• 化学式: C₂₄H₂₇NO₆
• 分子量: 425.481
• InChiKey: FZKPJPCBLFJJHO-FQEVSTJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  91.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (S)-2-(Benzhydrylidene-amino)-3-methoxycarbonyl-succinic acid 1-tert-butyl ester 4-methyl ester 、 碘甲烷 在 18-冠醚-6 、 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 5.0h， 生成 (S)-3-(Benzhydrylidene-amino)-2-methoxycarbonyl-2-methyl-succinic acid 4-tert-butyl ester 1-methyl ester
  参考文献：
  名称：

  Preparation of optically active β-carboxyaspartic acid derivatives via Pd(0)-catalyzed asymmetric substitution of Schiff base acetates

  摘要：

  Optically active beta-carboxyaspartic acid derivative 6 (77% ee) was obtained in 48% total yield from the coupling of Schiff base acetate 3 with sodium dimethyl malonate in the presence of 5% Pd(OAc)(2)-(2S,4S)-BPPM followed by a single recrystallization. Phase-transfer catalyzed alkylation of malonates 6 affords beta-substituted ASA derivatives 7 in excellent yield without racemization at the alpha-carbon. (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00048-1
• 作为产物：
  描述：

  Tert-butyl 2-(benzhydrylideneamino)-2-oxoacetate 在 palladium diacetate 、 三乙基硼氢化锂 、 (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 8.0h， 生成 (S)-2-(Benzhydrylidene-amino)-3-methoxycarbonyl-succinic acid 1-tert-butyl ester 4-methyl ester
  参考文献：
  名称：

  Efficient Catalytic Enantioselective Reaction of a Glycine Cation Equivalent with Malonate Anions via Palladium Catalysis

  摘要：

  The enantioselective alkylation of Schiff base acetates 1 with malonate types of stabilized carbon nucleophiles in the presence of a stable palladium source Pd(OAc)(2) and the chiral ligand (+)-BINAP was developed. The product 2, a protected beta-carboxyaspartic acid (ASA), was obtained in up to 85% enantiomeric excess by varying the ester protecting group on the substrate. The nature of the nucleophile has a significant effect on the enantioselectivity in this (2-aza-pi-allyl)palladium system. While a rapid chemical conversion was achieved with Schiff base benzoates 5, the enantioselectivity was insensitive to the leaving group used. An optically active substrate (51% ee) gave the same level of enantioselectivity as that obtained from the racemate. Temperature effects on the reaction were also studied; the best selectivity was obtained at 0 degrees C. A laboratory-scale reaction of the reactive nucleophile KCH(COOCH3)(2) with the tert-butyl ester substrate 1c gave, following a single recrystallization, product 2c with 95.5% ee in an overall chemical yield of 62%.

  DOI：

  10.1021/jo961869w

文献信息

• Efficient Catalytic Enantioselective Reaction of a Glycine Cation Equivalent with Malonate Anions <i>via</i> Palladium Catalysis
  作者：Martin J. O'Donnell、Ning Chen、Changyou Zhou、Angela Murray、Clifford P. Kubiak、Fan Yang、George G. Stanley

  DOI：10.1021/jo961869w

  日期：1997.6.13

  The enantioselective alkylation of Schiff base acetates 1 with malonate types of stabilized carbon nucleophiles in the presence of a stable palladium source Pd(OAc)(2) and the chiral ligand (+)-BINAP was developed. The product 2, a protected beta-carboxyaspartic acid (ASA), was obtained in up to 85% enantiomeric excess by varying the ester protecting group on the substrate. The nature of the nucleophile has a significant effect on the enantioselectivity in this (2-aza-pi-allyl)palladium system. While a rapid chemical conversion was achieved with Schiff base benzoates 5, the enantioselectivity was insensitive to the leaving group used. An optically active substrate (51% ee) gave the same level of enantioselectivity as that obtained from the racemate. Temperature effects on the reaction were also studied; the best selectivity was obtained at 0 degrees C. A laboratory-scale reaction of the reactive nucleophile KCH(COOCH3)(2) with the tert-butyl ester substrate 1c gave, following a single recrystallization, product 2c with 95.5% ee in an overall chemical yield of 62%.
• Preparation of optically active β-carboxyaspartic acid derivatives via Pd(0)-catalyzed asymmetric substitution of Schiff base acetates
  作者：Martin J. O'Donnell、Changyou Zhou、Ning Chen

  DOI：10.1016/0957-4166(96)00048-1

  日期：1996.3

  Optically active beta-carboxyaspartic acid derivative 6 (77% ee) was obtained in 48% total yield from the coupling of Schiff base acetate 3 with sodium dimethyl malonate in the presence of 5% Pd(OAc)(2)-(2S,4S)-BPPM followed by a single recrystallization. Phase-transfer catalyzed alkylation of malonates 6 affords beta-substituted ASA derivatives 7 in excellent yield without racemization at the alpha-carbon. (C) 1996 Elsevier Science Ltd