111633-59-1Relevant articles and documents
Overcoming product inhibition in catalysis of the intramolecular Schmidt reaction
Motiwala, Hashim F.,Fehl, Charlie,Li, Sze-Wan,Hirt, Erin,Porubsky, Patrick,Aube, Jeffrey
supporting information, p. 9000 - 9009 (2013/07/26)
A method for carrying out the intramolecular Schmidt reaction of alkyl azides and ketones using a substoichiometric amount of catalyst is reported. Following extensive screening, the use of the strong hydrogen-bond-donating solvent hexafluoro-2-propanol was found to be consistent with low catalyst loadings, which ranged from 2.5 mol % for favorable substrates to 25 mol % for more difficult cases. Reaction optimization, broad substrate scope, and preliminary mechanistic studies of this improved version of the reaction are described.
Intramolecular Schmidt reactions of alkyl azides with ketones: Scope and stereochemical studies
Milligan, Gregory L.,Mossman, Craig J.,Aubé, Jeffrey
, p. 10449 - 10459 (2007/10/03)
The intramolecular Schmidt reaction of alkyl azides and ketones has been demonstrated. The reaction is proposed to occur via initial attack of an azide on a ketone activated by a variety of protic or Lewis acids, including trifluoroacetic acid, titanium tetrachloride, and others. The resulting azidohydrin undergoes a direct rearrangement to afford the product amide and molecular nitrogen. When cyclic ketones are used, fused bicyclic lactams of types encountered in a wide variety of natural products are obtained. Although the distance allowed between the carbonyl group and the alkyl azide is quite restricted, the reaction is general with respect to the ketone component, including acyclic ketones and cyclic substrates ranging from standard to large ring sizes. The reaction also succeeds with aldehydes, although elimination or hydride migration products compete. In several cases examined the reaction was found to proceed with retention of configuration at the migrating carbon. Competing reactions with β-diketones and α,β-unsaturated ketones were found to predominate over ring expansion.
Bicyclization of aza-compounds by positive halide ions. II. Lactams and some related cyclizations
Elofson, Richard M.,Gadallah, Fahmi F.,Laidler, James K.
, p. 2770 - 2773 (2007/10/02)
Anodic oxidation of lactams in the presence of halide ions produced excellent yields of bicyclic compounds with reactants having rings in the range of eight to ten atoms (C7 to C9).Smaller rings did not react to form bicyclic products and larger rings gave reduced yields.Attempts were made to cyclize non-cyclic amides and to bicyclize cycloheptyl and cyclooctyl acetamide with limited success.
