tert-butyl α-azidoacrylate | 215181-48-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: tert-butyl α-azidoacrylate
• 英文别名: t-butyl α-azidoacrylate；tert-butyl 2-azidoacrylate；Tert-butyl 2-azidoprop-2-enoate
• CAS: 215181-48-9
• 化学式: C₇H₁₁N₃O₂
• 分子量: 169.183
• InChiKey: WPDRQPBCUNCNJO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  40.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl α-azidoacrylate 在 甲基溴化镁 、 Dimethylzinc 、 S-1,1'-联-2-萘酚 作用下， 以 甲苯 为溶剂， 反应 145.5h， 生成 tert-butyl (2R,6S)-2-[(2R,4S,5R)-5-hydroxy-2-phenyl-1,3-dioxan-4-yl]-1-azabicyclo[4.1.0]hept-3-ene-6-carboxylate
  参考文献：
  名称：

  Asymmetric Diels–Alder cycloadditions of d-erythrose 1,3-butadienes to achiral t-butyl 2H-azirine 3-carboxylate

  摘要：

  Two D-erythrose 1,3-butadienes were reacted with electrophilic achiral t-butyl 2H-azirine 3-carboxylate giving cycloadducts with good yields and moderate selectivity. The isomers could be separated to give the major (R)-isomers at C-2 in approximately 50% yield in both cases. Alternatively LACASA-DA methodology was applied to one of the reactions leading to homochiral (R)- and (S)-products by changing the chiral nature of an extra chiral BINOL inductor used. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.05.015
• 作为产物：
  描述：

  2,3-Diazido-propionic acid tert-butyl ester 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醚 为溶剂， 反应 0.25h， 以97%的产率得到tert-butyl α-azidoacrylate
  参考文献：
  名称：

  Generation and Diels-Alder reactions of t-butyl 2H-azirine-3-carboxylate

  摘要：

  The azirinyl ester 2 (R = Bu-t) has been generated by thermolysis of t-butyl 2-azidoacrylate. It is too unstable to allow its full characterisation but it has been intercepted by Diels-Alder cycloaddition to several dienes. Addition to a chiral diene 8 is highly diastereoselective. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01617-7

文献信息

• The azomethine ylide strategy for β-lactam synthesis. Azapenams and 1-azacephams
  作者：David Brown、Giles A. Brown、Mark Andrews、Jonathan M. Large、Dominique Urban、Craig P. Butts、Neil J. Hales、Timothy Gallagher

  DOI：10.1039/b203890k

  日期：——

  Reaction of the β-lactam-based oxazolidinone 5 with N-sulfonylimines provides the exo and endo azapenams 8 in 22–54% yield. The reactivity of 2H-azirines as 1,3-dipolarophiles towards β-lactam-based azomethine ylides derived from oxazolidinones 5 and 15 has also been evaluated. Azirines 11 and 12a provide cycloadducts 13a,b and 16 respectively, which incorporate the novel 2,6-diazatricyclo[4.2.0.02,4]octan-7-one ring system. These adducts were resistant towards C–N cleavage as the basis of an entry to 1-azacephams (1,5-diazabicyclo[4.2.0]octan-8-ones) 4. The use of the 3-(4-methoxyphenyl)-2H-azirine 19 provides a labile initial cycloadduct, which undergoes in situ ring-cleavage and further reaction to give the 2 ∶ 1 adduct 1-azacepham 22. The initial product is stable when 3-(4-nitrophenyl)-2H-azirine 23 is employed, and cycloadducts 24a and 24b are converted under mild reducing conditions to the 1-azacepham derivatives 25 and 26.

  β-内酰胺基恶唑啉酮5与N-磺酰亚胺反应生成外环和内环氮杂佩兰8，产率为22-54%。还评估了2H-氮杂环丙烷作为1,3-偶极亲偶极体与源自恶唑啉酮5和15的β-内酰胺基亚胺叶立德的反应活性。氮杂环丙烷11和12a分别生成含新型2,6-二氮杂三环[4.2.0.02,4]辛烷-7-酮环系的环加成物13a,b和16。这些加成物对C-N键断裂具有抗性，从而为获得1-氮杂头孢烷（1,5-二氮杂双环[4.2.0]辛烷-8-酮）4提供了途径。使用3-(4-甲氧苯基)-2H-氮杂环丙烷19得到了一个不稳定的初始环加成物，它通过原位环断裂和进一步反应生成2∶1加成物1-氮杂头孢烷22。当使用3-(4-硝基苯基)-2H-氮杂环丙烷23时，初始产物是稳定的，并且环加成物24a和24b在温和还原条件下转化为1-氮杂头孢烷衍生物25和26。
• Catalytic Enantioselective Reaction of 2<i>H</i>-Azirines with Thiols Using Cinchona Alkaloid Sulfonamide Catalysts
  作者：Shuichi Nakamura、Daiki Hayama、Masataka Miura、Tsubasa Hatanaka、Yasuhiro Funahashi

  DOI：10.1021/acs.orglett.7b04022

  日期：2018.2.2

  The first catalytic enantioselective reaction of 2H-azirines with thiols has been developed. The obtained aziridines can be converted to optically active oxazolines, aziridylamides, or α-sulfonyl esters. Transformation of these optically active aziridines showed that 2H-azirines act as β,β-dicarbocationic amine synthons.

  已经开发出2 H-叠氮基与硫醇的第一催化对映选择性反应。所获得的氮丙啶可以转化为光学活性的恶唑啉，叠氮基酰胺或α-磺酰基酯。这些旋光性氮丙啶的转化表明，2 H-氮丙啶可作为β，β-二碳并氨基胺合成子。
• Stereoselective cycloaddition of 1-glucosyl-1,3-butadienes with tert-butyl 2H-azirine-3-carboxylate, glyoxylates and imines
  作者：M.José Alves、I.G. Almeida、A. Gil Fortes、A.P. Freitas

  DOI：10.1016/s0040-4039(03)01696-4

  日期：2003.8

  Glucosyl dienes 1 have been reacted with the achiral 2H-azirine 4 and with glyoxylates, forming fused structures of type 5 and disaccharide-like compounds 7 with good to excellent selectivity. Glucosyl dienes 1 participated as dienophiles in reactions with Schiff bases derived from anilines forming isoquinolines 10 and 11. The diastereoselectivity of this reaction is poor.

  葡糖基二烯1已经与非手性2 H-叠氮基4和乙醛酸酯反应，形成了5型和二糖样化合物7的稠合结构，具有很好的选择性。葡萄糖基二烯1作为双亲体参与了与苯胺形成异喹啉10和11的席夫碱的反应。该反应的非对映选择性差。