(4R)-4-methoxycarbonylethynyl-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester | 173065-22-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4R)-4-methoxycarbonylethynyl-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester
• 英文别名: (R)-tert-butyl 4-(3-methoxy-3-oxoprop-1-yn-1-yl)-2,2-dimethyloxazolidine-3-carboxlate；tert-butyl (4R)-4-(3-methoxy-3-oxoprop-1-ynyl)-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 173065-22-0
• 化学式: C₁₄H₂₁NO₅
• 分子量: 283.324
• InChiKey: UKDUSUZBXIBEEC-SNVBAGLBSA-N

物化性质

• 沸点：
  380.0±42.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.53
• 重原子数：
  20.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  65.07
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (4R)-4-methoxycarbonylethynyl-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 palladium on activated charcoal 、 四(三苯基膦)钯 1,2,2,6,6-五甲基哌啶 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 三(2-呋喃基)膦 、 camphor-10-sulfonic acid 、 氢气 、 三甲基铝 、 三正丁基氢锡 、 sodium hydride 、 potassium carbonate 、 二甲基亚砜 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基乙酰胺 、 乙二醇 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， -10.0~130.0 ℃ 、8.27 MPa 条件下， 反应 68.0h， 生成
  参考文献：
  名称：

  Total synthesis of (+)-asperazine

  摘要：

  The first total synthesis of the structurally novel cyclotryptophan alkaloid asperazine is reported. The central step in the synthetic sequence is a diastereoselective intramolecular Heck reaction in which the substituent controlling stereoselection is external to the ring being formed. This synthesis confirmed the structure of (+)- asperazine (1) proposed by Crews and co- workers and provided material for additional biological studies. The in vitro cytotoxicity originally reported for the marine isolate was not confirmed with synthetic (+)- asperazine. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.05.127
• 作为产物：
  描述：

  (R)-(-)-2,2-dimethyl-3-tert-butoxycarbonyl-4-(β,β-dibromovinyl)oxazolidine 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.67h， 生成 (4R)-4-methoxycarbonylethynyl-2,2-dimethyl-oxazolidine-3-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  （R）-（-）-2,2-二甲基-3- t-丁氧基羰基-4-乙炔基-恶唑烷的立体选择性合成：合成一类新型取代炔烃的手性结构单元

  摘要：

  （R）-（-）-2，2-二甲基-3-叔丁氧基羰基-4-乙炔基-恶唑烷（3a）已通过两步方法由手性氨基醛（4）以高收率制备。已经研究了化合物（3a）的金属化以及随后与亲电试剂的反应，导致立体选择性合成了一系列新的取代炔烃，这些被认为是有用的具有生物学意义的化合物的前体

  DOI：

  10.1016/0040-4039(95)01725-w

文献信息

• A Macrocyclic Approach to Tetracycline Natural Products. Investigation of Transannular Alkylations and Michael Additions
  作者：Joseph S. Wzorek、Thomas F. Knöpfel、Ioannis Sapountzis、David A. Evans

  DOI：10.1021/ol302691j

  日期：2012.12.7

  presented. The pivotal intermediate is identified as macrocycle III. The two interior bonds (C4a–C12a and C5a–C11a) are to be constructed through sequential transannular Michael additions (III–II) and compression-promoted transannular isoxazole alkylations from intermediate II.

  提出了一种新的四环素核心结构方法。关键中间体被确定为大环III。两个内部键（C4a–C12a和C5a–C11a）将通过顺序的跨环Michael加成（III – II）和由中间体II压缩促进的跨环异恶唑烷基化来构建。
• Synthetic Elaboration of the Side Chain of (<i>R</i>)-2,2-Dimethyl-3-(<i>tert</i>-butoxycarbonyl)-4-ethynyloxazolidine:  A New Regio- and Stereoselective Strategy to δ-Functionalized β-Amino Alcohols
  作者：Gianna Reginato、Alessandro Mordini、Massimo Caracciolo

  DOI：10.1021/jo970619s

  日期：1997.9.1

  An investigation of the reactivity of ethynyloxazolidine 2 is presented. Functionalization at the acetylenic position has been found to occur very easily using the mild Sonogashira conditions. Addition of tributyltin cuprate 1 provided the corresponding stannylated (E)-ethenyloxazolidine 3, a new chiral building block which has been reacted with electrophiles under Pd catalysis. The reaction sequence occurred without racemization and showed an easy and mild procedure for the regio- and stereoselective synthesis of unsaturated amino alcohols.
• Stereoselective synthesis of (R)-(−)-2,2-dimethyl-3-t-butoxycarbonyl-4-ethynyl-oxazolidine: a chiral building block for the synthesis of a new class of substituted alkynes
  作者：Gianna Reginato、Alessandro Mordini、Alessandro Degl'Innocenti、Massimo Caracciolo

  DOI：10.1016/0040-4039(95)01725-w

  日期：1995.11

  (R)-(-)-2,2-Dimethyl-3-t-butoxycarbonyl-4-ethynyl-oxazolidine (3a) has been prepared in good yield from chiral aminoaldehyde (4) through a two step procedure. Metalation of compound (3a) and subsequent reaction with electrophiles has been investigated leading to the stereoselective synthesis of a new series of substituted alkynes which can be considered us useful precursors of compounds of biological

  （R）-（-）-2，2-二甲基-3-叔丁氧基羰基-4-乙炔基-恶唑烷（3a）已通过两步方法由手性氨基醛（4）以高收率制备。已经研究了化合物（3a）的金属化以及随后与亲电试剂的反应，导致立体选择性合成了一系列新的取代炔烃，这些被认为是有用的具有生物学意义的化合物的前体
• Total synthesis of (+)-asperazine
  作者：Steven P. Govek、Larry E. Overman

  DOI：10.1016/j.tet.2007.05.127

  日期：2007.8

  The first total synthesis of the structurally novel cyclotryptophan alkaloid asperazine is reported. The central step in the synthetic sequence is a diastereoselective intramolecular Heck reaction in which the substituent controlling stereoselection is external to the ring being formed. This synthesis confirmed the structure of (+)- asperazine (1) proposed by Crews and co- workers and provided material for additional biological studies. The in vitro cytotoxicity originally reported for the marine isolate was not confirmed with synthetic (+)- asperazine. (c) 2007 Elsevier Ltd. All rights reserved.