(S)-2-N-(benzyloxycarbonyl)amino-2-methyl-2-benzeneacetic acid | 169738-78-7

• 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-N-(benzyloxycarbonyl)amino-2-methyl-2-benzeneacetic acid
• 英文别名: Z-(S)-C^α-methylphenylglycine；(S)-N²-<(benzyloxy)carbonyl>-2-methyl-2-phenylglycine；N-carbobenzyloxy-2-(phenyl)alanine；(S)-2-(((Benzyloxy)carbonyl)amino)-2-phenylpropanoic acid；(2S)-2-phenyl-2-(phenylmethoxycarbonylamino)propanoic acid
• CAS: 169738-78-7
• 化学式: C₁₇H₁₇NO₄
• 分子量: 299.326
• InChiKey: IDNBEGJOWGRMLA-KRWDZBQOSA-N

物化性质

• 沸点：
  501.1±50.0 °C(Predicted)
• 密度：
  1.245±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  75.6
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-2-N-(benzyloxycarbonyl)amino-2-methyl-2-benzeneacetic acid 在 palladium on activated charcoal N-甲基吗啉 、 氢气 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 123.5h， 生成 (2S)-2-[[(2S)-2-amino-2-phenylpropanoyl]amino]-2-phenylpropanoic acid
  参考文献：
  名称：

  Exploring new dipeptides based on phenylglycine and Cα-methyl phenylglycine as hosts in inclusion resolutions

  摘要：

  Twelve homo-dipeptides derived from phenylglycine, Phg, and C-alpha-methyl phenylglycine, (alphaMe)Phg, were synthesized and tested as resolving agents in resolutions through selective crystallization of inclusion compounds. The 3D-structure of a hydrated (alphaMe)Phg dipeptide host was also solved by single crystal X-ray diffraction. These dipeptides were examined in the co-crystallization with 15 different racemic guests, mainly alcohols and sulfoxides. Next to confirming the literature results for the resolution Of methylphenylsulfoxide. a rather limited scope was found for new resolutions. Only racemic solketal could be resolved with H-(S)-(alphaMe)Phg-(S)-(alphaMe)Phg-OH in modest efficiency using various experimental techniques. This resolution was complicated by the formation of polymorphic host-guest crystals. Whereas a wide array of similar dipeptides could be explored as resolving agents, it is expected to be difficult to rationally design potentially Successful molecular structures. Compared to resolution by diastereomeric salt formation. inclusion complexes are less readily formed and therefore of a more limited scope and preparative applicability. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.044
• 作为产物：
  描述：

  (4S,5S)-4-[(S)-(1-amino-1-phenyl)ethyl]-5-benzyloxymethyl-2,2-dimethyl-1,3-dioxolane 在 对甲苯磺酸 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 20.17h， 生成 (S)-2-N-(benzyloxycarbonyl)amino-2-methyl-2-benzeneacetic acid
  参考文献：
  名称：

  Enantioselective synthesis of α,α-disubstituted-α-amino acids by a sequential nucleophilic addition to nitriles

  摘要：

  The sequential addition of two different nucleophiles to a tartaric acid-derived nitrile produced carbinamines. The adducts from chelation-controlled addition which are obtained in high diastereoselectivities and yields, were easily converted to alpha,alpha-disubstituted-alpha-amino acids. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(98)00503-1

文献信息

• <scp>L</scp>-Phenylalanine Cyclohexylamide: A simple and convenient auxiliary for the synthesis of optically pure α,α-disubstituted (<i>R</i>)- and (<i>S</i>)-amino acids
  作者：Daniel Obrecht、Udo Bohdal、Clemens Broger、Daniel Bur、Christian Lehmann、Ruth Ruffieux、Peter Schönholzer、Clive Spiegler、Klaus Müller

  DOI：10.1002/hlca.19950780305

  日期：1995.5.10

  synthesis of a series of optically pure α,α-disubstituted (R)- and (S)-amino acids of type 1, such as (R)- and (S)-2-methyl-phenylalanine (1a), (R)- and (S)-2-methyl-2-phenylglycine (1b), and (R)- and (S)-2-methylvaline (1c; Scheme 3). These amino acids were efficiently transformed into the suitably protected and activated amino acid building blocks (R)- and (S)-12b and (R)- and (S)-12c (Scheme 4) which are

  这项工作描述了L-苯丙氨酸环己基酰胺（5C），其为简单的，价格便宜，且功能强大的手性助剂为一系列光学纯α，α-二取代的（的合成- [R ）-和（小号）型的α-氨基酸1，这样如（R）-和（S）-2-甲基-苯丙氨酸（1a），（R）-和（S）-2-甲基-2-苯甘氨酸（1b）以及（R）-和（S）-2 -甲基缬氨酸（1c；方案3）。这些氨基酸被有效地转化为适当保护和活化的氨基酸构件（R）和（S）-12b以及（R）-和（S）-12c（方案4），它们已经准备好通过溶液或固相技术掺入肽中。基于属于非对映异构体肽系列6和7的6b，6c和7a的晶体结构，确定该系列的每个成员的绝对构型。对于6b和7a分别观察到II'和I型的β-转角几何形状，而6c以扩展构象结晶。讨论了侧链变化对这些三酰胺的构象和晶体堆积的影响。
• Role of Secondary Structure in the Asymmetric Acylation Reaction Catalyzed by Peptides Based on Chiral C^α-Tetrasubstituted α-Amino Acids
  作者：Fernando Formaggio、Alessandra Barazza、Andrea Bertocco、Claudio Toniolo、Quirinus B. Broxterman、Bernard Kaptein、Elena Brasola、Paolo Pengo、Lucia Pasquato、Paolo Scrimin

  DOI：10.1021/jo040107v

  日期：2004.5.1

  conformation. In this work, we have expanded the study of the Miller tetrapeptide by examining a set of analogues and shorter sequences (dipeptide amides), characterized by chiral Cα-tetrasubstituted α-amino acids of diverging bulkiness and optical configuration. Peptide synthesis in solution, conformational analysis by FT-IR absorption and 1H NMR techniques, and screening of catalytic activity as well have

  在最近的一系列论文中，Miller和他的同事们能够证明基于His（π-Me）的末端保护肽是不对称酰基转移反应的有效催化剂，可用于醇的动力学拆分。在一种支持结构的溶剂中，活性最高的化合物之一，即一个含Aib的四肽，被折叠成一个分子内双氢键结合的β-发夹基序，并带有II'型β-转角构象。在这项工作中，我们已经通过检查一组类似物和较短序列（二肽酰胺）的扩大了米勒四肽的研究，其特征在于，通过手性Ç α -tetrasubstitutedα氨基发散膨松性和光学配置的酸。溶液中的肽合成，通过FT-IR吸收和1进行构象分析还进行了1 H NMR技术和催化活性的筛选。我们的结果证实了β-发夹3D结构与肽的催化活性之间的密切关系。已经发现选择性比米勒化合物略高的四肽类似物。但是，末端保护的，工业上更具吸引力的二肽酰胺效果差。
• Enantioselective Synthesis of α-Quaternary Amino Acid Derivatives by Sequential Enzymatic Desymmetrization and Curtius Rearrangement of α,α-Disubstituted Malonate Diesters
  作者：Violeta Iosub、Anton R. Haberl、Jennifer Leung、Michael Tang、Kannan Vembaiyan、Masood Parvez、Thomas G. Back

  DOI：10.1021/jo902584r

  日期：2010.3.5

  A convenient and versatile enantioselective synthesis of biologically important α-quaternary amino acid derivatives was based on the sequential double alkylation or arylation of dimethyl malonate, followed by desymmetrization with porcine liver esterase (PLE) and Curtius rearrangement. The PLE-mediated hydrolysis of the prochiral dialkylated malonate diesters produced the corresponding chiral half-esters

  生物学上重要的α-季氨基酸衍生物的方便且通用的对映选择性合成是基于丙二酸二甲酯的顺序双烷基化或芳基化，然后用猪肝酯酶（PLE）进行不对称化和Curtius重排。PLE介导的前手性二烷基丙二酸二酯的水解以高收率和对映体过量43％至> 98％产生了相应的手性半酯。在用苄醇或胺捕获中间异氰酸酯后，后一种产物的库尔修斯重排得到相应的Cbz-保护的氨基酯或脲。在五个示例中，主要产品的绝对构型是通过转化为具有已知比旋光度的化合物确定的，
• Synthesis of alpha--amino-alpha, alpha'- dihaloketones and process for the preparation of beta--amino acid derivatives by the use of the same
  申请人：Kaneka Corporation

  公开号：US20030158436A1

  公开（公告）日：2003-08-21

  The present invention provides a commercially profitable process for producing a &bgr;-amino acid ester derivative which comprises reacting an &agr;-amino acid ester derivative with a base and a dihalomethane, reacting the same with a lithium amide and an alkyllithium in succession, and treating the reaction product with an acid in an alcohol.

  本发明提供了一种商业上有利可图的制备β-氨基酸酯衍生物的方法，包括将α-氨基酸酯衍生物与碱和二卤甲烷反应，然后依次与锂酰胺和烷基锂反应，最后在醇中用酸处理反应产物。
• SYNTHESIS OF $g(a)-AMINO-$g(a)',$g(a)'-DIHALOKETONES AND PROCESS FOR THE PREPARATION OF $g(b)-AMINO ACID DERIVATIVES BY THE USE OF THE SAME
  申请人：KANEKA CORPORATION

  公开号：EP1078919A1

  公开（公告）日：2001-02-28

  The present invention provides a commercially profitable process for producing a β-amino acid ester derivative which comprises reacting an α-amino acid ester derivative with a base and a dihalomethane, reacting the same with a lithium amide and an alkyllithium in succession, and treating the reaction product with an acid in an alcohol.

  本发明提供了一种生产β-氨基酸酯衍生物的商业盈利工艺 其中包括使 α-氨基酸酯衍生物与碱和二卤甲烷反应、 使其依次与锂酰胺和烷基锂反应 并用醇中的酸处理反应产物。