贝克曼重排,Beckmann重排,Beckmann Rearrangement
由酸引起的肟的重排以生成酰胺。
该反应与Hofmann和Schmidt反应以及Curtius重排有关，因为形成正电性氮以引发烷基迁移。
贝克曼重排的机制
肟类化合物通常具有很高的反转阻挡，因此可以预见该反应通过肟羟基的质子化，然后烷基取代基“反”迁移到氮中进行。N-O键随着水的排出而同时裂解，从而避免形成游离腈。
Recent Literature
An efficient Beckmann rearrangement at room temperature involves an eosin Y catalyzed, visible-light-mediated in situ formation of the Vilsmeier-Haack reagent from CBr4 and a catalytic amount of DMF. This operationally simple method for the activation of ketoximes avoids the need for any corrosive, water-sensitive reagents and elevated temperatures.
V. P. Srivastava, A. K. Yadav, L. D. S. Yadav, Synlett, 2014, 25, 665-670.
Dichloroimidazolidinedione-Activated Beckmann Rearrangement of Ketoximes for Accessing Amides and Lactams
Y. Gao, J. Liu, Z. Li, T. Guo, S. Xu, H. Zhu, F. Wei, S. Chen, H. Gebru, K. Guo, J. Org. Chem., 2018, 83, 2040-2049.
Beckmann Rearrangement of Ketoximes to Lactams by Triphosphazene Catalyst
M. Hashimoto, Y. Obora, S. Sakaguchi, Y. Ishii, J. Org. Chem., 2008, 73, 2894-2897.
Efficient Iodine-Mediated Beckmann Rearrangement of Ketoximes to Amides under Mild Neutral Conditions
N. C. Ganguly, P. Mondal, Synthesis, 2010, 3705-3709.
Beckmann Rearrangement of Oximes under Very Mild Conditions
L. De Luca, G. Giacomelli, A. Porcheddu, J. Org. Chem., 2002, 67, 6272-6274.
Bromodimethylsulfonium Bromide-ZnCl2: A Mild and Efficient Catalytic System for Beckmann Rearrangement
L. D. S. Yadav, R. Patel, V. P. Srivastava, Synthesis, 2010, 1771-1776.
Au/Ag-Cocatalyzed Aldoximes to Amides Rearrangement under Solvent- and Acid-Free Conditions
R. S. Ramón, J. Bosson, S. Díez-González, N. Marion, S. P. Nolan, J. Org. Chem., 2010, 75, 1197-1202.
Beckmann reaction of oximes catalysed by chloral: mild and neutral procedures
S. Chandrasekhar, K. Gopalaiah, Tetrahedron Lett., 2003, 44, 755-756.
Mercury-Catalyzed Rearrangement of Ketoximes into Amides and Lactams in Acetonitrile
C. Ramalingan, Y.-T. Park, J. Org. Chem., 2007, 72, 4536-4538.
Solvent-Free and One-Step Beckmann Rearrangement of Ketones and Aldehydes by Zinc Oxide
H. Sharghi, M. Hosseini, Synthesis, 2002, 1057-1059.