tert-butyl-acetyloxydiphenylmethyleneaminoacetate | 176965-32-5

• 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: tert-butyl-acetyloxydiphenylmethyleneaminoacetate
• 英文别名: Tert-butyl 2-acetyloxy-2-(benzhydrylideneamino)acetate
• CAS: 176965-32-5
• 化学式: C₂₁H₂₃NO₄
• 分子量: 353.418
• InChiKey: VXBPOQRNZQZPHF-UHFFFAOYSA-N

物化性质

• 沸点：
  437.8±45.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  65
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl-acetyloxydiphenylmethyleneaminoacetate 在 palladium diacetate 、 18-冠醚-6 、 sodium hydride 、 potassium carbonate 、 (2S,4S)-4-二苯基膦-2-(二苯基膦甲基)-N-叔丁氧羰基-吡咯烷 作用下， 以 乙腈 为溶剂， 反应 8.25h， 生成 (S)-2-Allyl-3-(benzhydrylidene-amino)-2-methoxycarbonyl-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：

  N-二苯亚甲基-甘氨酸叔丁酯 、 lead(IV) tetraacetate 以 二氯甲烷 为溶剂， 反应 5.0h， 以92%的产率得到tert-butyl-acetyloxydiphenylmethyleneaminoacetate
  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

文献信息

• The Enantioselective Synthesis of α-Amino Acid Derivatives via Organoboranes
  作者：Martin J. O'Donnell、Mark D. Drew、Jeremy T. Cooper、Francisca Delgado、Changyou Zhou

  DOI：10.1021/ja017522e

  日期：2002.8.1

  Optically active (S)-α-amino acids are prepared in 54−95% ee (12 cases) by reaction of the Schiff base acetate of glycine tert-butyl ester with B-alkyl-9-BBN derivatives in the presence of the Cinc...

  通过甘氨酸叔丁酯的席夫碱乙酸酯与 B-烷基-9-BBN 衍生物在 Cinc 存在下反应，以 54-95% ee（12 例）制备光学活性 (S)-α-氨基酸...
• Acyclic Stereoselective Boron Alkylation Reactions for the Asymmetric Synthesis of β-Substituted α-Amino Acid Derivatives
  作者：Martin J. O'Donnell、Jeremy T. Cooper、Mary M. Mader

  DOI：10.1021/ja0298794

  日期：2003.3.1

  Optically active syn- or anti-β-substituted-α-amino acid derivatives are prepared in 94 to ≥99% ee and 66−98% ds by reaction of the Schiff base acetate of glycine tert-butyl ester with chiral, nonracemic B-alkyl-9-BBN derivatives in the presence of the Cinchona alkaloid, cinchonidine (CdOH) or cinchonine (CnOH), base, and lithium chloride.

  通过甘氨酸叔丁酯的席夫碱乙酸酯与手性非外消旋 B-反应，以 94% 至≥99% ee 和 66-98% ds 制备光学活性的顺式或反式 β-取代的-α-氨基酸衍生物在金鸡纳生物碱、辛可尼丁 (CdOH) 或辛可宁 (CnOH)、碱和氯化锂存在下的烷基-9-BBN 衍生物。
• Synthesis of 3-aminoaspartic acid derivatives from glycine precursors
  作者：Yu Chen、Andrei K. Yudin

  DOI：10.1016/s0040-4039(03)01122-5

  日期：2003.6

  3-Aminoaspartic acid derivatives 3 have been synthesized via stereoselective alkylation of α-acetyloxyglycine Schiff base 2 with the enolate of glycine anion equivalent 1 as a carbon nucleophile in the presence of Pd(OAc)2 and BINAP at room temperature. High chemical yields and moderate stereoselectivities were observed. The enantiomeric excess of the dl diastereomer can be increased to 95% after a

  在室温下，在Pd（OAc）2和BINAP存在下，通过将甘氨酸阴离子当量1的烯酸酯作为碳亲核试剂，通过α-乙酰氧基甘氨酸Schiff碱2的立体选择性烷基化反应合成了3-氨基天冬氨酸衍生物3。观察到高化学产率和中等立体选择性。在异丙醇和己烷中重结晶一次后，dl非对映异构体的对映体过量可增加至95％。
• De Meijere, Armin; Ernst, Katrin; Zuck, Bernd, European Journal of Organic Chemistry, 1999, # 11, p. 3105 - 3115
  作者：De Meijere, Armin、Ernst, Katrin、Zuck, Bernd、Brandl, Melanie、Kozhushkov, Sergei I.、Tamm, Markus、Yufit, Dmitrii S.、Howard, Judith A. K.、Labahn, Thomas

  DOI：——

  日期：——
• 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%.