tert-butyl N-[(1S)-1-(5-bromo-4-cyano-1,3-oxazol-2-yl)-2-methylpropyl]carbamate | 218769-27-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: tert-butyl N-[(1S)-1-(5-bromo-4-cyano-1,3-oxazol-2-yl)-2-methylpropyl]carbamate
• CAS: 218769-27-8
• 化学式: C₁₃H₁₈BrN₃O₃
• 分子量: 344.208
• InChiKey: XOCNLGRVFPNHFR-VIFPVBQESA-N

物化性质

• 沸点：
  436.3±40.0 °C(Predicted)
• 密度：
  1.38±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  88.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl N-[(1S)-1-(5-bromo-4-cyano-1,3-oxazol-2-yl)-2-methylpropyl]carbamate 在 双(乙腈)氯化钯(II) 、 三溴化硼 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 生成 [(S)-2-(4-Benzyloxy-3-iodo-phenyl)-1-((S)-1-{4-cyano-5-[1-(2-methoxy-phenyl)-vinyl]-oxazol-2-yl}-2-methyl-propylcarbamoyl)-ethyl]-carbamic acid tert-butyl ester
  参考文献：
  名称：

  Macrocyclic Triarylethylenes via Heck Endocyclization:  A System Relevant to Diazonamide Synthesis

  摘要：

  DOI：

  10.1021/jo981791e
• 作为产物：
  描述：

  [(S)-1-(5-Amino-4-cyano-oxazol-2-yl)-2-methyl-propyl]-carbamic acid tert-butyl ester 在 亚硝酸特丁酯 、 copper(ll) bromide 作用下， 以 乙腈 为溶剂， 以55%的产率得到tert-butyl N-[(1S)-1-(5-bromo-4-cyano-1,3-oxazol-2-yl)-2-methylpropyl]carbamate
  参考文献：
  名称：

  Macrocyclic Triarylethylenes via Heck Endocyclization:  A System Relevant to Diazonamide Synthesis

  摘要：

  DOI：

  10.1021/jo981791e

文献信息

• A Concise Formal Synthesis of Diazonamide A by the Stereoselective Construction of the C10 Quaternary Center
  作者：Cheng-Kang Mai、Matthew F. Sammons、Tarek Sammakia

  DOI：10.1002/anie.200906318

  日期：2010.3.22

  Protecting groups are overrated! A formal total synthesis of diazonamide A is described. The key step in this synthesis is an intramolecular SNAr reaction between an oxindole and a bromooxazole. Interestingly, this reaction proceeds best using the mild base Na2CO3, and with no protecting groups on the oxindole nitrogen atom or phenol groups of the cyclization precursor.

  保护团体被高估了！描述了重氮酰胺 A 的正式全合成。该合成的关键步骤是羟吲哚和溴恶唑之间的分子内 S N Ar 反应。有趣的是，该反应最好使用弱碱 Na 2 CO 3 进行，并且环化前体的羟吲哚氮原子或酚基团上没有保护基团。
• Approaches to the quaternary stereocentre and to the heterocyclic core in diazonamide A using the Heck reaction and related coupling reactions
  作者：James E. M. Booker、Alicia Boto、Gwydion H. Churchill、Clive P. Green、Matthew Ling、Graham Meek、Jaya Prabhakaran、David Sinclair、Alexander J. Blake、Gerald Pattenden

  DOI：10.1039/b609604b

  日期：——

  In model studies towards the quaternary centre at the heart of diazonamide A (early structure 2; revised structure 1), cyclisations of the alkene-substituted iodoaryls 4, 13, 18 and 23, under Heck reaction conditions, were shown to lead to the corresponding benzodihydrofuran 5, benzofuranone 14 and the oxindoles 19 and 24 respectively, in 50–80% yield. Further manipulation of the benzodihydrofuran 5 then led to the intermediates 30, 33 and 39, which make up parts of the oxazole–indole heterocyclic core in diazonamide A. Attempts to perform a corresponding 13-exo-trig Heck cyclisation from the precursor 46a, prepared from 44 and 45, leading to 47 were not successful. A similar outcome was obtained during attempts to effect Heck cyclisations from the ester 57 and the related ether 59. Treatment of the chromene-substituted iodoaryl 62 with Pd(OAc)2, PPh3 and Ag2CO3 led to the spirocycle 64 as a crystalline solid. X-Ray crystal structure analysis established that the quaternary centre in 64 had the same configuration as that present in diazonamide A (1).

  在对二氮酰胺A（早期结构2；修订后的结构1）中四次碳中心进行的模型研究中，显示在Heck反应条件下，碱基取代的碘芳烃4、13、18和23的环化反应分别生成了相应的苯并二氢呋喃5、苯并噁唑酮14以及氧吲哚19和24，得率为50-80%。进一步操作苯并二氢呋喃5后，得到了中间体30、33和39，它们构成了二氮酰胺A中噁唑–吲哚杂环核心的一部分。从前体46a（由44和45制备而成）进行相应的13-exo-trig Heck环化反应以生成47的尝试未能成功。在试图从酯57和相关醚59进行Heck环化时也得到了类似的结果。用Pd(OAc)2、PPh3和Ag2CO3处理含克罗门的碘芳烃62，生成了结晶固体螺环64。X射线晶体结构分析确定64中的四次碳中心的构型与二氮酰胺A（1）中的构型相同。
• Total Synthesis of Nominal Diazonamides-Part 1: Convergent Preparation of the Structure Proposed for (−)-Diazonamide A
  作者：Jing Li、Susan Jeong、Lothar Esser、Patrick G. Harran

  DOI：10.1002/1521-3773(20011217)40:24<4765::aid-anie4765>3.0.co;2-1

  日期：2001.12.17
• α-Arylation of 3-Aryloxindoles
  作者：Cheng-Kang Mai、Matthew F. Sammons、Tarek Sammakia

  DOI：10.1021/ol100666v

  日期：2010.5.21

  A versatile method for the synthesis of 3,3-diaryloxindoies via Pd-catalyzed alpha-arylations or an SNAr reaction is described. The reaction proceeds using mild base, is tolerant of a variety of functional groups, and is capable of preparing hindered all-carbon quaternary centers.
• Macrocyclic Triarylethylenes via Heck Endocyclization:  A System Relevant to Diazonamide Synthesis
  作者：Susan Jeong、Xin Chen、Patrick G. Harran

  DOI：10.1021/jo981791e

  日期：1998.11.1