(2S,3R)-3-hydroxy-N-methoxy-N,2-dimethylpent-4-enamide | 724460-32-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3R)-3-hydroxy-N-methoxy-N,2-dimethylpent-4-enamide
• CAS: 724460-32-6
• 化学式: C₈H₁₅NO₃
• 分子量: 173.212
• InChiKey: WHGWTVNIYFHOSZ-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R)-3-hydroxy-N-methoxy-N,2-dimethylpent-4-enamide 在 甲醇 、 4-二甲氨基吡啶 、 二异丁基氢化铝 、 三乙胺 、 二异丙胺 、 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazolium chloride 、 copper(l) chloride 、 copper(I) bromide 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 27.0h， 生成
  参考文献：
  名称：

  NHC–Cu-Catalyzed Protoboration of Monosubstituted Allenes. Ligand-Controlled Site Selectivity, Application to Synthesis and Mechanism

  摘要：

  Two types of NHC-Cu complexes catalyze protoborations of terminal allenes to afford valuable 1,1- or trisubstituted vinylboron species with high site selectivity and stereoselectivity. The scope of the method, application to natural product synthesis, and mechanistic basis for the observed selectivity trends are presented.

  DOI：

  10.1021/ol4004178
• 作为产物：
  描述：

  二甲羟胺盐酸盐 、 <4S,3(2S,3R)>-4-benzyl-3-(3-hydroxy-2-methyl-4-pentenoyl)-2-oxazolidinone 在 三甲基铝 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.0h， 以66%的产率得到(2S,3R)-3-hydroxy-N-methoxy-N,2-dimethylpent-4-enamide
  参考文献：
  名称：

  Enyne与Diene RCM合成FR182877 A环的环戊烯衍生物

  摘要：

  合成了FR182877的A环，以ent -4-b ，c为例，其中涉及烯键RCM作为关键步骤。对烯炔与二烯RCM形成环戊烯衍生物的系统比较表明，即使在这种环尺寸下，后者的复分解过程也更容易进行。

  DOI：

  10.1021/jo049557d

文献信息

• Total Synthesis and Structural Assignment of Curvicollide C
  作者：Valeska von Kiedrowski、Florian Quentin、Martin Hiersemann

  DOI：10.1021/acs.orglett.7b02126

  日期：2017.8.18

  The first total synthesis of (+)-curvicollide C has been accomplished. Cross-metathesis and Julia–Kocienski olefination were instrumental in the synthesis of 1,3-diene segments and allowed for a ternary-convergent synthetic design. A full structural assignment is proposed for (−)-curvicollide C, a uniquely structured polyketide of fungal origin.

  （+）-curvicollide C的第一个全合成反应已经完成。交叉复分解和Julia-Kocienski烯烃化在1,3-二烯链段的合成中发挥了作用，并允许进行三元收敛的合成设计。建议对（-）-curvicollide C（一种真菌来源的独特结构的聚酮化合物）进行完整的结构分配。
• Substrate-controlled stereoselectivity in the Yamamoto aldol reaction
  作者：Nadin Schläger、Andreas Kirschning

  DOI：10.1039/c2ob26185e

  日期：——

  The Yamamoto aldol reaction is a vinylogous aldol reaction that relies on bulky aluminium-based Lewis acids. These activate both the aldehyde as well as become part of the enolate moiety. The report discloses the first detailed study on the substrate-controlled Yamamoto aldol reaction in which 2,3-syn and 2,3-anti disubstituted aldehydes serve as the stereodirecting elements. The “size” of the substituent in the β-position strongly determines the facial selectivity of enolate addition to the aldehyde. Large substituents favour formation of 1,3-syn diols while slim alkynyl groups preferentially lead to 1,3-anti products.

  山本 aldol 反应是一种依赖于笨态铝基路易斯酸的传统 aldol 反应。这些路易斯酸不仅激活醛，还成为烯醇负离子部分的一部分。该报告首次详细研究了底物控制的山本 aldol 反应，其中 2,3-syn 和 2,3-anti 二取代醛作为立体导向元素。β-位取代基的“大小”强烈决定了烯醇添加至醛的面选择性。大的取代基有利于形成 1,3-syn 二醇，而纤细的炔基团则优先生成 1,3-anti 产品。
• Enyne versus Diene RCM in the Synthesis of Cyclopentene Derivatives toward the A Ring of FR182877
  作者：Jacques-Alexis Funel、Joëlle Prunet

  DOI：10.1021/jo049557d

  日期：2004.6.1

  The A ring of FR182877, exemplified by ent-4-b,c, has been synthesized, involving an enyne RCM as the key step. A systematic comparison of enyne vs diene RCM for the formation of cyclopentene derivatives showed that the latter metathesis proceeds much more easily even for this ring size.

  合成了FR182877的A环，以ent -4-b ，c为例，其中涉及烯键RCM作为关键步骤。对烯炔与二烯RCM形成环戊烯衍生物的系统比较表明，即使在这种环尺寸下，后者的复分解过程也更容易进行。
• Total synthesis of (+)-calyculin A
  作者：David A. Evans、James R. Gage、James L. Leighton

  DOI：10.1021/ja00050a024

  日期：1992.11

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.
• NHC–Cu-Catalyzed Protoboration of Monosubstituted Allenes. Ligand-Controlled Site Selectivity, Application to Synthesis and Mechanism
  作者：Fanke Meng、Byunghyuck Jung、Fredrik Haeffner、Amir H. Hoveyda

  DOI：10.1021/ol4004178

  日期：2013.3.15

  Two types of NHC-Cu complexes catalyze protoborations of terminal allenes to afford valuable 1,1- or trisubstituted vinylboron species with high site selectivity and stereoselectivity. The scope of the method, application to natural product synthesis, and mechanistic basis for the observed selectivity trends are presented.