Hypervalent iodine compounds are known for their extensive use as potentialo xidants in organic synthesis.I ns pite of the similar reactivity with transitionm etals,h ypervalent iodine reagents are more preferred because of their environmental sustainability.A mong several types of hypervalent iodine reagents,t rivalent organoiodine(III) reagents are highly popular due to their easy accessibility,s tability and controlled oxidizing reactivity.A lso, iodine(III) reagents are commerciallya vailable andi nexpensive. Amines and amidesr eact with iodine(III) oxidants in some specificw ay to provide ad ivalent electrophilic ionic species known as an itrenium ion. Depending on the nature and stability of the nitrenium ion, numerous oxidative transformations to generate valuable functional molecules have been reported.T his review encompassesd iscussionsa bout hypervalent organo iodine(III)-enabled organic transformationsw ith the involvemento fanitrenium ion as an intermediate. Figure1.Ionic electrophilic speciesw ith 6v alance electrons.
The field of hypervalent iodine chemistry has been prevalent since 1886. Its journey from obscurity to coming into the limelight has witnessed many effective transformations which have benefited the synthetic community at large. The reactivity of primary amines with hypervalent iodine reagents causes difficulty in synthetic outcome or not feasible due to high exothermicity of amine iodine which is an acid base reaction. This minireview highlights the worthwhile reactivity of hypervalent iodine reagents with aromatic and aliphatic primary amines. Some recent literature has been discussed to make a clear understanding on how such high reactivity of primary amine is controlled by introducing modulation in either substrate or reaction conditions, most of which are carried out under ambient reaction conditions.
Here we report a metal-free C-N coupling reaction for carbazole synthesis by distal (- meta) C-H bond functionalization. Nitrenium ion, a potential synthetic intermediate, was generated in situ from reactions of iodine(III) reagents and biarylsulfonanilides. Following, nitrenium ions were used for intramolecular dehydrogenative C-N coupling reactions via 1,2-alkyl (methyl or ethyl) migration by the expense of C-H bond functionalization at the distal position toward synthesis of 1,2,4-trialkyl-substituted carbazoles. The iodine(III) condition was either maintained by using a stoichiometric amount of phenyliodine diacetate (PIDA) or in-situ generated from iodobenzene (PhI)- meta-chloroperbenzoic acid ( mCPBA) combination.
The enlarged landscape of catalysis lies in the heart of chemistry. As the journey has set a milestone in organic synthesis, its darker side has not entered into the limelight. Studies disclose that the reported reactions by using catalysts were also attainable in the absence of catalysts in many cases. This article presents a literature collection that includes the significance of control experiments in hydrofunctionalization reactions. Systematic analysis reveals that the catalysts are ambiguous and might be unessential in chemical reactions enlisted here.
Aliphatic iodination via mechanochemistry is a mammoth challenge due to the high polarizability and weak electrophilicity of iodonium cation (I + ), and low bond dissociation energy of carbon iodine bond. Herein, the synthesis is demonstrated of oxazoline derivatives from Nallyl benzamides via mechanochemical cascaded cyclization and halogenation using N-iodo-and N-bromosuccinimides, respectively, as bifunctional reagents.
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