N-benzyl-N-benzyloxycarbonyl-L-alaninal | 139190-71-9

• 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-benzyl-N-benzyloxycarbonyl-L-alaninal
• 英文别名: N-benzyl-N-Cbz-L-alaninal；benzyl N-benzyl-N-[(2S)-1-oxopropan-2-yl]carbamate
• CAS: 139190-71-9
• 化学式: C₁₈H₁₉NO₃
• 分子量: 297.354
• InChiKey: ODKRFYRAXDGOOX-HNNXBMFYSA-N

物化性质

• 沸点：
  438.2±44.0 °C(Predicted)
• 密度：
  1.155±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-benzyl-N-benzyloxycarbonyl-L-alaninal 在 palladium on activated charcoal 正丁基锂 、 氢气 、 碳酸氢钠 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 乙酸乙酯 为溶剂， 反应 5.0h， 生成 (1S,2S)-N-benzyl-N-[2-(5-methylfuran-2-yl)-2-hydroxy-1-methylethyl]carbamic acid tert-butyl ester
  参考文献：
  名称：

  Asymmetric addition of 2-methylfuran and its lithiated derivative to variously N,N-protected l-alaninals

  摘要：

  The asymmetric reaction of 2-methylfuran 2a and its lithiated derivative 2b with N,N-diprotected L-alaninals 1a-c, carried out under high pressure conditions in the presence of Lewis acid-catalyst, are described. For aldehyde la two diastereoisomeric adducts anti-3a and syn-3a were formed, with predominance of the former. In the case of aldehydes 1b and 1c only the anti-diastereoisomers 3b or 3c were formed, but accompanied by two diastereoisomeric oxazolidinones trans-4 and cis-4. The absolute configuration (via X-ray analysis of anti-5 and chemical correlations) and the extent of asymmetric induction were established. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00545-1
• 作为产物：
  描述：

  N-ALPHA-苄基-L-丙氨酸甲酯 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 、 锂硼氢 、 碳酸氢钠 、 sodium bromide 作用下， 以 四氢呋喃 、 乙醇 、 水 、 乙酸乙酯 、 甲苯 为溶剂， 反应 23.0h， 生成 N-benzyl-N-benzyloxycarbonyl-L-alaninal
  参考文献：
  名称：

  通过TEMPO氧化制备光学活性α-氨基醛的有效温和方法

  摘要：

  TEMPO氧化方法已成功地用于制备各种受保护的旋光性α-氨基醛，且不发生外消旋作用，并且收率很高。

  DOI：

  10.1016/s0040-4020(98)00299-3

文献信息

• Synthesis of α-amino and α-alkoxy aldehydes via oxoammonium oxidation
  作者：M. Robert Leanna、Thomas J. Sowin、Howard E. Morton

  DOI：10.1016/s0040-4039(00)61180-2

  日期：1992.8

  Oxoammonium oxidation (TEMPO, 1) of various optically active α-amino and α-alkoxy alcohols affords the corresponding aldehydes in good yield and high enantiomeric purity.

  各种旋光性α-氨基和α-烷氧基醇的氧铵氧化（TEMPO，1）以高收率和高对映体纯度提供相应的醛。
• On the Stereochemical Divergence in the Conjugate Addition of Lithium Dimethylcuprate/Trimethylsilyl Chloride to γ-Alkoxy and γ-Ureido α,β-Unsaturated Esters
  作者：Stephen Hanessian、Kenzo Sumi

  DOI：10.1055/s-1991-28396

  日期：——

  A comparative study was made of the reaction of chiral non-racemic γ-alkoxy and γ-ureido-α,β-unsaturated esters with lithium dimethylcuprate in the presence of trimethylsilyl chloride. The possible origins of the anti- and syn-additions respectively are discussed and rationalized.

  在三甲基氯硅烷存在下，对手性非气相δ-烷氧基和δ-脲基δ,δ-不饱和酯与二甲基杯酸锂的反应进行了比较研究。分别讨论了反加成和合成加成的可能起源，并使之合理化。
• The stereochemical course of addition of allyltrimethylsilane to protected l-alaninals and l-serinals in the presence of Lewis acids. Total synthesis of cis-(2R,3S)-3-hydroxyproline
  作者：D. Gryko、P. Prokopowicz、J. Jurczak

  DOI：10.1016/s0957-4166(02)00255-0

  日期：2002.6

  l-alaninals and l-serinals was investigated and high levels of asymmetric induction were achieved. Stereochemical models for rationalisation of the results obtained are proposed. cis-(2R,3S)-3-Hydroxyproline was synthesised starting from N-Cbz,O-TBS-l-serinal, in which the crucial step involves addition of allyltrimethylsilane to the aldehyde in the presence of SnCl4.

  研究了路易斯酸对将烯丙基三甲基硅烷添加到各种受保护的l-丙氨酸和l-丝氨酸中的非对映选择性的影响，并实现了高水平的不对称诱导。提出了立体化学模型，用于合理化所获得的结果。顺式-（2 R，3 S）-3-羟基脯氨酸从N -Cbz，O -TBS-1-丝氨酸开始合成，其中关键步骤涉及在SnCl 4存在下向烯醛中添加烯丙基三甲基硅烷。
• Diastereoselective addition of vinylmagnesium halides to variously N-mono- and N,N-diprotected l-alaninals
  作者：Dorota Gryko、Zofia Urbańczyk-Lipkowska、Janusz Jurczak

  DOI：10.1016/s0957-4166(97)00558-2

  日期：1997.12

  Diastereoselective C-2-elongation processes of N-mono- 1a-c and N,N-diprotected 1d-f L-alaninals, using vinylmagnesium bromide and chloride, are described. A substantial difference between effects of the N-protecting groups replacing either one or two amino protons was observed. (C) 1997 Elsevier Science Ltd. All rights reserved.
• ——
  作者：Dorota Gryko、Janusz Jurczak

  DOI：10.1002/1522-2675(20001004)83:10<2705::aid-hlca2705>3.0.co;2-y

  日期：2000.10.4

  Diastereoselective C-3-clongation processes of N-Boc-, N-Z-, N-Bn-N-Boc-, and N-Bn-N-Z-L-alaninals (Boc = BuOCO, Z PhCH2OCO, Bn = PhCH2) using various allyl reagents, such as allyl bromide in the presence of Zn/aqueous NH4Cl solution. of SnCl2 . 2 H2O/NaI or of Mg/CuCl2 . 2 H2O, as well as allyltrichlorosilane. are described. A substantially different influence of the N-protecting groups replacing either one or two amino protons was observed, allowing the selective synthesis of either the syn- or anti-diastereoisomer as a major product.