(2S)-(+)-2-羟基-2-苯基乙酰氧肟酸 | 124097-40-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (2S)-(+)-2-羟基-2-苯基乙酰氧肟酸
• 英文名称: (2S)-(+)-2-hydroxy-2-phenylacetohydroxamic acid
• 英文别名: (S)-2-hydroxy-2-phenylacetohydroxamic acid；(S)-(-)-Mandelohydroxamic acid；l-Mandelohydroxamic acid；(2S)-N,2-dihydroxy-2-phenylacetamide
• CAS: 124097-40-1
• 化学式: C₈H₉NO₃
• 分子量: 167.164
• InChiKey: MLFRTFJESPROFS-ZETCQYMHSA-N

物化性质

• 密度：
  1.348±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  69.6
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S)-(+)-2-羟基-2-苯基乙酰氧肟酸 在 palladium dihydroxide 4-二甲氨基吡啶 、 sodium amalgam 、 N-溴代丁二酰亚胺(NBS) 、 氢气 、 四丁基高碘酸铵 作用下， 以 1,4-二氧六环 、 乙醇 、 水 为溶剂， 反应 54.0h， 生成 Acetic acid (1S,2S,3R,4R,5S)-3-acetoxy-2-bromo-4-hydroxymethyl-5-phenylacetylamino-cyclopentyl ester
  参考文献：
  名称：

  Enantioselective Approaches to Aminocyclopentitols:  A Total Synthesis of (+)-6-Epitrehazolin and a Formal Total Synthesis of (+)-Trehazolin

  摘要：

  Potent inhibitors of trehalase, such as trehazolin and its congeners, represent an attractive approach to the design of effective new insect control agents. In this report, enantioselective total syntheses of (-)-6-epitrehazolin and (+)-trehazolin were achieved using the asymmetric heterocycloaddition between [(benzyloxy)methyl]cyclopentadiene and the acylnitroso compound arising from in situ oxidation of (S)-mandelohydroxamic acid with tetrabutylammonium periodate. Further function- alization of the resulting 3,4,5-trisubstituted cyclopentene, either involving osmylation or epoxidation of the double bond, efficiently created pentasubstituted cyclopentanes. Introduction of the quaternary carbon in both synthesis targets was achieved via stereoselective osmylation of an intermediate 2,3,4,5-substituted 1-methylenecyclopentane.

  DOI：

  10.1021/jo980050a
• 作为产物：
  描述：

  L-扁桃酸甲酯 在 羟胺 作用下， 以 甲醇 为溶剂， 生成 (2S)-(+)-2-羟基-2-苯基乙酰氧肟酸
  参考文献：
  名称：

  α-羟基酰基亚硝基化合物的狄尔斯-阿尔德反应中的不对称诱导

  摘要：

  能够形成分子内氢键的瞬态手性α-羟基酰基亚硝基化合物（2）与环戊二烯和环己-1,3-二烯立体选择性地反应；后者的二烯的环加合物（6）和（）-扁桃酸的亚硝基衍生物已被转化为已知的（-）-恶嗪衍生物（9）。

  DOI：

  10.1016/s0040-4039(00)82298-4

文献信息

• Chiral Diels–Alder reaction between cyclopentadiene and nitroso derivatives: thermal isomerisation/racemisation of the adducts
  作者：Jean-Marc Heuchel、Sébastien Albrecht、Christiane Strehler、Albert Defoin、Céline Tarnus

  DOI：10.1016/j.tetasy.2012.09.005

  日期：2012.11

  Cyclopentadiene nitroso adducts 1a and ent-1a were synthesised in good yields and good enantiomeric excess from chiral chloro-nitroso derivatives 4 and 5 in the d-mannose and d-ribose series, respectively. The thermal racemisation of these adducts occurred below room temperature. Some other chiral Diels–Alder nitroso adducts were prepared in the d-mandelic, l-prolinol and d-O-methylprolinol series

  从d-甘露糖和d-核糖系列的手性氯亚硝基衍生物4和5分别以高收率和良好的对映异构体合成环戊二烯亚硝基加合物1a和ent - 1a。这些加合物的热消旋作用发生在室温以下。制备了其他一些手性Diels-Alder亚硝基加合物，分别为d-扁桃，l-脯氨醇和d- O-甲基脯氨醇，并根据N取代对它们进行了热异构化。从ent - 1a提出了手性酰胺基-环戊烯醇（+）- 2b（一种重要的生物有趣化合物的简单前体）的简单合成方法。
• Single and double asymmetric induction in Diels-Alder cycloadditions with chiral acylnitroso dienophiles
  作者：Albert Defoin、Joaquim Pires、Isabelle Tissot、Théophile Tschamber、Daniel Bur、Margareta Zehnder、Jacques Streith

  DOI：10.1016/s0957-4166(00)80021-x

  日期：1991.1

  achiral 1-silyloxybutadiene 1a with the chiral acyinitroso dienophile 2a gave cycloadduct 4 in high diastereomeric excess (d.e. > 98 %), a result which is undoubtedly due to the C-2 symmetrical chiral dimethylpyrrolidine inductor. Excellent d.e. was also observed when the (R)-prolinol dienophile 2d was reacted with the chiral diene 1b (d.e. = 96 %), whereas cycloaddition of the (S) enantiomer 2e with 1b gave

  非手性1-甲硅烷氧基丁二烯1a与手性酰基亚硝基二亲二烯体2a的Diels-Alder反应产生高非对映异构体过量的环加合物4（de＞ 98％），这无疑是由于C-2对称的手性二甲基吡咯烷诱导剂。当（R）-脯氨醇双亲二烯体2d与手性二烯1b反应时（de = 96％），也观察到了极好的de（de），而（S）对映异构体2e与1b的环加成反应仅引起较差的不对称诱导（de= 4％）。后两个示例很好地说明了“不匹配对”（1b / 2d）与“不匹配对”（1b / 2e）对双重不对称感应的影响。本文所有报道的Diels-Alder环加成均是区域特异性的。
• Kirby, Gordon W.; Nazeer, Muhammad, Journal of the Chemical Society. Perkin transactions I, 1993, # 13, p. 1397 - 1402
  作者：Kirby, Gordon W.、Nazeer, Muhammad

  DOI：——

  日期：——
• Controlled racemization and asymmetric transformation of α-substituted carboxylic acids in the melt
  作者：Eelco J. Ebbers、Gerry J.A. Ariaans、Alle Bruggink、Binne Zwanenburg

  DOI：10.1016/s0957-4166(99)00387-0

  日期：1999.9

  The racemization and asymmetric transformation of a series of cx substituted carboxylic acids, viz. mandelic acid, hydratropic acid, ibuprofen and naproxen, were studied. Several racemization methods for mandelic acid were studied and it was found that base-catalyzed racemization in aprotic polar solvents was the most efficient method. Moreover, a fast and mild base-catalyzed racemization reaction in the melt was developed. DBN turned out to be a very efficient racemizing base for the substrates studied. Combination of the base-catalyzed racemization in the melt with known resolution processes resulted in crystallization-induced asymmetric transformations. Treating racemic ibuprofen or hydratropic acid with 1.5-2.5 equivalents of enantiopure alpha-methylbenzylamine and a catalytic amount of DBN resulted in the isolation of enantiomerically enriched ibuprofen or hydratropic acid with ees of up to 75% and almost quantitative yields. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Asymmetric induction in the diels-alder reactions of α-hydroxyacylnitroso compounds
  作者：Gordon W. Kirby、Muhammad Nazeer

  DOI：10.1016/s0040-4039(00)82298-4

  日期：——

  Transient, chiral α-hydroxyacylnitroso compounds (2), able to form intramolecular hydrogen bonds, react stereoselectively with cyclopentadiene and cyclohexa-1,3-diene; the cycloadduct (6) of the latter diene and the nitroso derivative of ()-mandelic acid has been converted into the known (-)-oxazine derivative (9).

  能够形成分子内氢键的瞬态手性α-羟基酰基亚硝基化合物（2）与环戊二烯和环己-1,3-二烯立体选择性地反应；后者的二烯的环加合物（6）和（）-扁桃酸的亚硝基衍生物已被转化为已知的（-）-恶嗪衍生物（9）。