scholarly journals Heterocyclic group transfer reactions with I(iii) N-HVI reagents: access to N-alkyl(heteroaryl)onium salts via olefin aminolactonization

2021 ◽  
Author(s):  
Anthony F. Tierno ◽  
Jennifer C. Walters ◽  
Andres Vazquez-Lopez ◽  
Xiao Xiao ◽  
Sarah E. Wengryniuk
Keyword(s):  
Transfer Reactions ◽  
Group Transfer ◽  
Mild Conditions ◽  
Onium Salts ◽  
Heterocyclic Group

Complex N-alkyl (heteroaryl)onium salts are accessed via heterocyclic group transfer reactions of N-ligated I(iii) reagents with alkenoic acids. The reactions proceed in excellent yields, under mild conditions, and with broad substrate scope.

scholarly journals Heterocyclic Group Transfer Reactions with I(III) N-HVI Reagents: Access to N-Alkyl (Heteroaryl)onium Salts via Olefin Aminolactonization

2020 ◽  
Author(s):  
Anthony F. Tierno ◽  
Jennifer C. Walters ◽  
Andres Vazquez-Lopez ◽  
Xiao Xiao ◽  
Sarah Wengryniuk
Keyword(s):  
Hypervalent Iodine ◽  
Alkyl Aryl ◽  
Diversity Oriented Synthesis ◽  
Group Transfer ◽  
Broad Scope ◽  
Nucleophilic Displacement ◽  
Onium Salts ◽  
Recent Emergence ◽  
Iodonium Salt ◽  
Heterocyclic Group

<p>Pyridinium and related N-alkyl (heteroaryl)onium salts are versatile synthetic intermediates in organic chemistry, with applications ranging from ring functionalizations to provide diverse piperidine scaffolds to their recent emergence as radical precursors in deaminative cross couplings. Despite their ever-expanding applications, methods for their synthesis have seen little innovation, continuing to rely on a limited set of decades old transforms. Herein, we leverage (bis)cationic nitrogen-ligated I(III) hypervalent iodine reagents, or <i>N</i>-HVIs, as “heterocyclic group transfer reagents” to provide access to a broad scope of (heteroaryl)onium salts via the aminolactonization of alkenoic acids. The reactions proceed in excellent yields, under mild conditions, and are capable of incorporating a broad scope of sterically and electronically diverse aromatic heterocycles. The <i>N</i>-HVI reagents can be generated <i>in situ</i>, the products isolated via simple trituration, and subsequent derivatizations demonstrate the power of this platform for diversity-oriented synthesis of 6-membered nitrogen heterocycles. Mechanistic studies indicate the reaction proceeds via initial olefin activation followed by lactonization and subsequent intermolecular nucleophilic displacement of an (alkyl)(aryl)iodonium salt hypernucleofuge.</p>

scholarly journals Heterocyclic Group Transfer Reactions with I(III) N-HVI Reagents: Access to N-Alkyl (Heteroaryl)onium Salts via Olefin Aminolactonization

2020 ◽  
Author(s):  
Anthony F. Tierno ◽  
Jennifer C. Walters ◽  
Andres Vazquez-Lopez ◽  
Xiao Xiao ◽  
Sarah Wengryniuk
Keyword(s):  
Hypervalent Iodine ◽  
Alkyl Aryl ◽  
Diversity Oriented Synthesis ◽  
Group Transfer ◽  
Broad Scope ◽  
Nucleophilic Displacement ◽  
Onium Salts ◽  
Recent Emergence ◽  
Iodonium Salt ◽  
Heterocyclic Group

<p>Pyridinium and related N-alkyl (heteroaryl)onium salts are versatile synthetic intermediates in organic chemistry, with applications ranging from ring functionalizations to provide diverse piperidine scaffolds to their recent emergence as radical precursors in deaminative cross couplings. Despite their ever-expanding applications, methods for their synthesis have seen little innovation, continuing to rely on a limited set of decades old transforms. Herein, we leverage (bis)cationic nitrogen-ligated I(III) hypervalent iodine reagents, or <i>N</i>-HVIs, as “heterocyclic group transfer reagents” to provide access to a broad scope of (heteroaryl)onium salts via the aminolactonization of alkenoic acids. The reactions proceed in excellent yields, under mild conditions, and are capable of incorporating a broad scope of sterically and electronically diverse aromatic heterocycles. The <i>N</i>-HVI reagents can be generated <i>in situ</i>, the products isolated via simple trituration, and subsequent derivatizations demonstrate the power of this platform for diversity-oriented synthesis of 6-membered nitrogen heterocycles. Mechanistic studies indicate the reaction proceeds via initial olefin activation followed by lactonization and subsequent intermolecular nucleophilic displacement of an (alkyl)(aryl)iodonium salt hypernucleofuge.</p>

scholarly journals Bicyclo[2.2.0]hexene derivatives as a proaromatic platform for group transfer and chemical sensing

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Bin Wu ◽  
Jianing Wang ◽  
Xingchen Liu ◽  
Rong Zhu
Keyword(s):  
Intramolecular Charge Transfer ◽  
Solid Phase ◽  
Functional Materials ◽  
High Thermal Stability ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Mild Conditions ◽  
Synthetic Utility ◽  
Electrophilic Reagents ◽  
Sensing Application

AbstractHere we report the design, preparation, synthetic utility, and sensing application of a class of proaromatic structures, namely bicyclo[2.2.0]hexene (BCH) derivatives. Building on a valence isomerism concept, they feature modular and easy synthesis as well as high thermal stability, and can be oxidatively activated under mild conditions. New alkyl transfer reactions using BCHs as a radical donor have been developed to showcase the utility of their proaromaticity. Moreover, the redox-triggered valence isomerization of a quinoline-derived BCH led to colorimetric and fluorescent responses toward vapors of electrophilic reagents in solution and solid phase, respectively. This optical response was shown to involve a 1,3-cyclohexadiene structure that possesses an intramolecular charge transfer excited state with interesting aggregation induced emission (AIE) character. Thus, the potential of BCHs has been demonstrated as a versatile platform for the development of new reagents and functional materials.

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bipyridine cocrystal with their crystal structures

2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Transfer Reaction ◽  
Acyl Transfer ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Hydrogen Bonding Interactions ◽  
Benzoyl Group ◽  
The Stability ◽  
Group Migration

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

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