N-acetoxymethanesulfonamide

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: N-acetoxymethanesulfonamide
• 英文别名: Methanesulfonamido acetate；methanesulfonamido acetate
• 化学式: C₃H₇NO₄S
• 分子量: 153.159
• InChiKey: YDKYBUBLUHEPGA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  80.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-acetoxymethanesulfonamide 、 甲苯 在 copper(II) tetrafluroborate hexahydrate 、 (1R,2R)-N,N'-di(2',3',4',5',6'-pentafluorobenzylidene)-1,2-diaminocyclohexane 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以40%的产率得到N-苄基甲烷磺酰胺
  参考文献：
  名称：

  基于羟胺的胺化试剂的非定向，Cu催化的sp3 C–H胺化：催化和机理研究

  摘要：

  This work demonstrates the use of hydroxyl amine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.

  DOI：

  10.1021/acs.organomet.7b00003
• 作为产物：
  描述：

  N-hydroxylmethanesulfonamide 、 乙酰氯 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.25h， 以3.1 g的产率得到N-acetoxymethanesulfonamide
  参考文献：
  名称：

  基于羟胺的胺化试剂的非定向，Cu催化的sp3 C–H胺化：催化和机理研究

  摘要：

  This work demonstrates the use of hydroxyl amine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.

  DOI：

  10.1021/acs.organomet.7b00003

文献信息

• Stereoselective Synthesis of<i>cis</i>-2,5-Disubstituted Pyrrolidines via Copper-Catalyzed Cyclization of Alkenes
  作者：Sai-Hu Cai、Bing-Chao Da、Jia-Hui Zhou、Yun-He Xu、Teck-Peng Loh

  DOI：10.1002/cjoc.201600380

  日期：2016.11

  An efficient methodology for the stereoselective synthesis of cis‐2,5‐disubstituted pyrrolidines using copper catalyst was developed. The corresponding cis‐2,5‐disubstituted pyrrolidines could be obtained in reasonable yields and with good stereoselectivities in the presence of 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine as ligand and 1‐methyl‐2‐pyrrolidinone as solvent.

  开发了一种使用铜催化剂立体选择性合成顺式-2,5-二取代吡咯烷的有效方法。在4,4'-二叔丁基-2,2'-联吡啶作为配体和1-甲基-2-基吡啶存在下，可以以合理的收率和良好的立体选择性获得相应的顺式-2,5-二取代的吡咯烷。吡咯烷酮作为溶剂。
• Nondirected, Cu-Catalyzed sp³ C–H Aminations with Hydroxylamine-Based Amination Reagents: Catalytic and Mechanistic Studies
  作者：Anqi Wang、Nicholas J. Venditto、Julia W. Darcy、Marion H. Emmert

  DOI：10.1021/acs.organomet.7b00003

  日期：2017.4.10

  This work demonstrates the use of hydroxyl amine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.