<(-)-1R-Menthyloxy>carbonyl-azid | 118013-05-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: <(-)-1R-Menthyloxy>carbonyl-azid
• 英文别名: L-menthyl azidoformate；((-)-1R-Menthyloxy)carbonyl-azid；[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] N-diazocarbamate
• CAS: 118013-05-1
• 化学式: C₁₁H₁₉N₃O₂
• 分子量: 225.291
• InChiKey: CYTQLNAKXFAUQL-KXUCPTDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  40.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  <(-)-1R-Menthyloxy>carbonyl-azid 在 正丁基锂 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 52.5h， 生成
  参考文献：
  名称：

  Asymmetric electrophilic amination of enolates by a chiral N-alkoxycarbonyloxaziridine

  摘要：

  A new chiral 3-aryl-N-alkoxycarbonyloxaziridine; derived from menthol, has been prepared and tested as a reagent for asymmetric electrophilic amination of enolates. The aminated products were obtained in low diastereoselectivities of up to 21% d.e. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00104-5
• 作为产物：
  描述：

  (1R,2S,5R)-Menthyl chloroformate 在 sodium azide 、 四丁基碘化铵 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 16.0h， 以60%的产率得到<(-)-1R-Menthyloxy>carbonyl-azid
  参考文献：
  名称：

  Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??

  摘要：

  The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2. But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloadditon is modestly stereoselective by steric hindrance within the cyclic enolether 3b. Very small de-values were found with chiral substituents in the acylazide 13.The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.

  DOI：

  10.1002/prac.19943360807

文献信息

• An Efficient One-Pot Synthesis of Azidoformates from Alcohols Using Triphosgene: Synthesis of<i>N</i>-Carbobenzyloxy Azetidin-2-ones
  作者：A. R. Deshmukh、R. T. Patil、Ghazala Parveen、V. K. Gumaste、B. M. Bhawal

  DOI：10.1055/s-2002-33512

  日期：——

  Division of Organic Chemistry (Synthesis), National Chemical Laboratory, Pune - 411 008, IndiaFax [phone]; E-mail: [e-mail] 30 May 2002Synlett 2002, No. 9, Print: 02 09 2002. Art Id.1437-2096,E;2002,0,09,1455,1458,ftx,en;G15202ST.pdf. © Georg Thieme Verlag Stuttgart · New YorkISSN 0936-5214Abstract: An efficient use of triphosgene for the preparation of var-ious azidoformates

  有机化学部（合成），国家化学实验室，浦那 - 411 008，印度传真 [phone]；电子邮件：[e-mail] 30 May 2002Synlett 2002, No. 9, Print: 02 09 2002. Art Id.1437-2096,E;2002,0,09,1455,1458,ftx,en ;G15202ST.pdf。© Georg Thieme Verlag Stuttgart · New YorkISSN 0936-5214 摘要：描述了一种有效利用三光气从醇和叠氮化钠制备各种叠氮甲酸酯的方法。该方法适用于包括葡萄糖二丙酮在内的各种手性醇，得到相应的叠氮甲酸酯。其中一种叠氮甲酸酯已成功用于合成N-羧苄氧基-内酰胺类化合物。 关键词：叠氮甲酸酯，醇，叠氮化钠，三光气，azetidin-2-one
• Enzymatic C(sp³)-H Amination: P450-Catalyzed Conversion of Carbonazidates into Oxazolidinones
  作者：Ritesh Singh、Joshua N. Kolev、Philip A. Sutera、Rudi Fasan

  DOI：10.1021/cs5018612

  日期：2015.3.6

  stereoselectivity. Mechanistic studies and KIE experiments show that the C–H activation step in these reactions is rate-limiting and proceeds in a stepwise manner, namely, via hydrogen atom abstraction followed by radical recombination. This study expands the reactivity scope of P450-based catalysts in the context of nitrene transfer transformations and provides first-time insights into the mechanism

  细胞色素 P450 酶可以有效促进碳叠氮化物底物的活化和环化，通过分子内氮宾 C-H 插入反应生成恶唑烷酮。对底物范围的研究表明，虽然苄基/烯丙基 C-H 键最容易被这些生物催化剂胺化，但更强的二级 C-H 键也易于官能化。利用这种“非天然”反应性并在基于指纹的预测的辅助下，可以鉴定细菌 P450 CYP102A1 的改进活性位点变体，以介导两种具有高区域和立体选择性的萜烯天然产物的氨基官能化。机理研究和 KIE 实验表明，这些反应中的 C-H 活化步骤是限速的，并且以逐步的方式进行，即通过氢原子抽提，然后进行自由基重组。这项研究扩大了基于 P450 的催化剂在氮烯转移转化方面的反应范围，并首次深入了解 P450 催化的 C-H 胺化反应的机理。
• DILLEN, JAN L. M.;METH-COHN, OTTO;MOORE, CLIVE;ROOYEN, PETRUS H. VAN, TETRAHEDRON, 44,(1988) N 11, C. 3127-3138
  作者：DILLEN, JAN L. M.、METH-COHN, OTTO、MOORE, CLIVE、ROOYEN, PETRUS H. VAN

  DOI：——

  日期：——
• Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??
  作者：Karin Buck、Dirk Jacobi、Yvette Pl�gert、Werner Abraham

  DOI：10.1002/prac.19943360807

  日期：——

  The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2. But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloadditon is modestly stereoselective by steric hindrance within the cyclic enolether 3b. Very small de-values were found with chiral substituents in the acylazide 13.The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.
• Asymmetric electrophilic amination of enolates by a chiral N-alkoxycarbonyloxaziridine
  作者：Alan Armstrong、Mark A. Atkin、Steven Swallow

  DOI：10.1016/s0957-4166(01)00104-5

  日期：2001.3

  A new chiral 3-aryl-N-alkoxycarbonyloxaziridine; derived from menthol, has been prepared and tested as a reagent for asymmetric electrophilic amination of enolates. The aminated products were obtained in low diastereoselectivities of up to 21% d.e. (C) 2001 Elsevier Science Ltd. All rights reserved.