2-叔丁基-2-苯基-1-(4-甲苯磺酰基)氮丙啶 | 136175-22-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 中文名称: 2-叔丁基-2-苯基-1-(4-甲苯磺酰基)氮丙啶
• 英文名称: 2-tert-butyl-2-phenyl-1-(4-tolylsulfonyl)aziridine
• 英文别名: 1-(tert-butyl)-1-phenyl-N-tosylaziridine；2-Tert-butyl-1-(4-methylphenyl)sulfonyl-2-phenylaziridine
• CAS: 136175-22-9
• 化学式: C₁₉H₂₃NO₂S
• 分子量: 329.463
• InChiKey: FBBJACUMSRJCSV-UHFFFAOYSA-N

物化性质

• 沸点：
  450.9±55.0 °C(Predicted)
• 密度：
  1.190±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-叔丁基-2-苯基-1-(4-甲苯磺酰基)氮丙啶 在 蒽 、 sodium 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以86%的产率得到2-Phenyl-2-tert-butylaziridin
  参考文献：
  名称：

  Nitrogen-sulfur cleavage is faster than homolytic ring opening in single-electron transfer to some N-sulfonylaziridines. Competition between SN2 and SET

  摘要：

  The radical anions of the N-sulfonylaziridines, 1a,b and 3 undergo N-S cleavage in place of homolytic ring opening as is demonstrated by reactions with anthracenide A.- Nucleophilic ring opening of the sulfonylaziridines 1a,b and 3 by the carbanions AH-,X-, and Fl- of dihydroanthracene, xanthene, and fluorene, respectively, proceeds with the expected regioselectivity and is slow enough to allow some competition by a single-electron transfer (SET) initiated N-S cleavage, which provides the desulfonated aziridines and bixanthenyl X-X or bifluorenyl Fl-Fl, respectively. The SET path is favored by light. The competition is in favor of SET to the exclusion of the nucleophilic opening when trityl anion reacts with 1a. The twice-found byproducts 11 and 12 require the azirine intermediate 15, which is, at least formally, generated by elimination of TsH from 1a in a non-SET reaction.

  DOI：

  10.1021/jo00024a028
• 作为产物：
  描述：

  2,2,2-三甲基苯乙酮 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 、 硫酸锰水合物 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 37.5h， 生成 2-叔丁基-2-苯基-1-(4-甲苯磺酰基)氮丙啶
  参考文献：
  名称：

  缺电子烯烃配体通过镍催化交叉偶联生成季碳

  摘要：

  已开发出镍催化的 Negishi 与 1,1-二取代苯乙烯基氮丙啶的交叉偶联。该方法通过提供季碳的具有挑战性的还原消除来提供有价值的 β-取代苯乙胺。一种新型缺电子烯烃配体 Fro-DO 被证明对于通过 β-H 消除实现 CC 键形成的高速率和化学选择性至关重要。该配体易于获取、稳定，并为反应发现和优化提供了模块化框架。我们预计这些属性，再加上配体赋予金属不同的电子特性，将支持使用既定配体以前不可能实现的新转化的发明。

  DOI：

  10.1021/jacs.5b02503

文献信息

• Two-Step 1,2-Shifts by β-Cleavage of Carbenium Ions and Recombination in Friedel−Crafts Reactions of 2-<i>tert</i>-Butyl-1-tosylaziridines¹
  作者：Konstantinos Bellos、Helmut Stamm

  DOI：10.1021/jo980774m

  日期：1998.10.1

  AlCl3-induced ring cleavage of two 2-tert-butyl-1-tosylaziridines in benzene (PhH) or anisole (AnH) generates carbenium ions (CIs). Subsequent neopentyl rearrangement forms CIs 3a,b, whose beta-cleavage generates +CH2NTsAlC3- (14) and an alkene. The intermediate 14 can recombine with the alkene at either C=C carbon, resulting in a reversal of the cleavage (3a,b) or in a formal 1,2-shift (CIs 12a,b). AnH rapidly removes 14 from these interconverting systems by formation of a methoxybenzylamide species that undergoes fragmentation into TsNHAlCl3- and methoxybenzyl cation, which gives dianisylmethane (main product). PhH reacts slowly with 14, leaving CIs 3a,b and 12a,b more time for other reactions. Unreacted 14 can even be trapped by AnH at the end of a PhH run. Protonation of each alkene forms N-free CIs that react with PhH and AnH. Replacing tosyl in one of the aziridines by benzoyl makes the beta-cleavage markedly slower than both the classic phenyl shift and the internal trapping of CIs.
• Reactions of a tertiary carbon carrying a tert-butyl Group: Acid-catalyzed alcoholyses of activated aziridines with and without solvent assistance.
  作者：Konstantinos Bellos、Helmut Stamm

  DOI：10.1021/jo00122a057

  日期：1995.9

  Acid-catalyzed ring opening of tosylated and acylated 2-tert-butylaziridines 1 (2-phenyl) and 2 (2-benzyl) generates carbenium ions 18 (from 1) and 19 (from 2) which rearrange by a neopentyl rearrangement to carbenium ions 20 (18 --> 20) and 21 (19 --> 21). Reactions of 18-21 farm the final products: (1) deprotonation yields allylamides, homoallylamides, and enamides; (2) external trapping of 18 or 19 by a solvent molecule yields ethers; (3) internal trapping (only acylated 1 and 2) yields oxazolines and dihydrooxazines. The amount of external trapping with 1a,b depends on the activation: 1a (tosyl activation) yields more methyl ether (75% vs 51%) than 1b (benzoyl), but 1a yields less isopropyl ether (0% vs 25%) than 1b. The latter finding is in accord with an intramolecular interaction of the carbenium center of 18a with one of the tosyl oxygen atoms provided that this interaction distorts the carbenium plane to a pyramid which sterically retards external trapping. The former finding is not observed with 2a and 2b. This points to at least some methanol-assisted ring opening of 1a-H+ that must be supported by a benzylic effect. The required conformation of the phenyl ring is fixed in 1a-H+ (N-protonation and bulky SO2 cis to phenyl) but not in 1b-H+ (O-protonation and planar nitrogen conformation).
• Stamm, Helmut, Journal fur Praktische Chemie (Weinheim), 1999, vol. 341, # 4, p. 319 - 331
  作者：Stamm, Helmut

  DOI：——

  日期：——