Catalytic β C–H amination via an imidate radical relay

Abstract

An iodine-catalyzed strategy for β C–H amination of alcohols is enabled by a chemo-, regio-, and stereo-selective H-atom transfer mechanism.

Synthesis of Oxazoline and Oxazole Derivatives by Hypervalent-Iodine-Mediated Oxidative Cycloaddition Reactions

“…14,51,53,54 Numerous synthetic strategies for the construction of the oxazoline ring have been explored. Particularly important are synthetic approaches using hypervalent iodine reagents, such as (diacetoxyiodo)arenes, [55][56][57][58][59][60][61][62][63][64][65] iodosylarenes, 66 (difluoroiodo)arenes, 67 in situ generated iodine(III) species, [68][69][70][71][72][73] or iodonium ylides. 74,75 This section covers synthetic methodologies for the preparation of various oxazoline derivatives from appropriate substrates using hypervalent iodine species.…”

“…Nagib and co-workers reported the use of acetyl hypoiodite generated from (diacetoxyiodo)benzene and elemental iodine in the cyclization reaction of imidate compounds leading to the respective oxazolines in good yields. 65 The obtained products could be converted into -amino alcohols by acidic hydrolysis.…”

Recent Advances in Rapid Synthesis of Non-proteinogenic Amino Acids from Proteinogenic Amino Acids Derivatives via Direct Photo-Mediated C–H Functionalization

“…Proline (Scheme 48a), phenylalanine, and leucine (Scheme 48b) derivatives were regioselectively aminated with triflamide (TfNH 2 ), a catalytic amount of molecular iodine, and PhI(O 2 CAr) 2 in 59-68% yields. Mechanically, ArCO 2 I was formed from PhI(O 2 CAr) 2 and molecular iodine [98], which subsequently reacted with TfNH 2 to generate the N-iodinated species. Photo-induced homolysis and the following HAT process would yield the iodo-substituted amino acids.…”

Practical, metal-free remote heteroarylation of amides via unactivated C(sp3)–H bond functionalization

“…Therefore, amides are usually elaborated to other surrogates that deliver amidyl radicals under mild conditions 6,7. Elegant modifications of HLF reaction from Suárez8 and others9,10 convert the amide N–H bonds to amidyl radicals by homolysis of the in situ formed N–I species. But those reactions are limited to the cyclization to afford the pyrrolidine derivatives (Scheme 1c).…”