56222-10-7Relevant articles and documents
Decarboxylative Ritter-Type Amination by Cooperative Iodine (I/III)─Boron Lewis Acid Catalysis
Narobe, Rok,Murugesan, Kathiravan,Schmid, Simon,K?nig, Burkhard
, p. 809 - 817 (2022/01/15)
Recent years have witnessed important progress in synthetic strategies exploiting the reactivity of carbocations via photochemical or electrochemical methods. Yet, most of the developed methods are limited in their scope to certain stabilized positions in molecules. Herein, we report a metal-free system based on the iodine (I/III) catalytic manifold, which gives access to carbenium ion intermediates also on electronically disfavored benzylic positions. The unusually high reactivity of the system stems from a complexation of iodine (III) intermediates with BF3. The synthetic utility of our decarboxylative Ritter-type amination protocol has been demonstrated by the functionalization of benzylic as well as aliphatic carboxylic acids, including late-stage modification of different pharmaceutical molecules. Notably, the amination of ketoprofen was performed on a gram scale. Detailed mechanistic investigations by kinetic analysis and control experiments suggest two mechanistic pathways.
Transition-Metal- and Halogen-Free Oxidation of Benzylic sp 3 C-H Bonds to Carbonyl Groups Using Potassium Persulfate
Hu, Yixin,Zhou, Lihong,Lu, Wenjun
supporting information, p. 4007 - 4016 (2017/08/29)
Aryl carbonyl compounds including acetophenones, benzophenones, imides, and benzoic acids are prepared from benzyl substrates using potassium persulfate as oxidant with catalytic pyridine in acetonitrile under mild conditions. Neither transition metals nor halogens are involved in the reactions.
Dynamic path bifurcation in the Beckmann reaction: Support from kinetic analyses
Yamamoto, Yutaro,Hasegawa, Hiroto,Yamataka, Hiroshi
experimental part, p. 4652 - 4660 (2011/07/29)
The reactions of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles when the migrating groups have reasonable stability as cations. The reactions of oxime sulfonates of 1-substituted-phenyl-2-propanone derivatives (7-X) and related substrates (8-X, 9a-X) in aqueous CH3CN gave both rearrangement products (amides) and fragmentation products (alcohols), the ratio of which depends on the system; the reactions of 7-X gave amides predominantly, whereas 9a-X yielded alcohols as the major product. The logk-logk plots between the systems gave excellent linear correlations with slopes of near unity. The results support the occurrence of path bifurcation after the rate-determining TS of the Beckmann rearrangement/fragmentation reaction, which has previously been proposed on the basis of molecular dynamics simulations. It was concluded that path-bifurcation phenomenon could be more common than thought and that a reactivity-selectivity argument based on the traditional TS theory may not always be applicable even to a well-known textbook organic reaction.
