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WIREs Comput Mol Sci
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Hypercoordinate iodine(III) promoted reactions and catalysis: an update on current mechanistic understanding

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Mild and environment friendly hypercoordinate iodine compounds exhibit promising reactivities resembling that of transition metal catalysts. Hypercoordinate iodine reagents or catalysts are increasingly been employed in contemporary organic synthesis. However, mechanistic insights on such reactions continue to remain rather limited. Recent advances in the mechanistic understanding on a selected set of reactions involving hypercoordinate iodine form the main theme of this review. An overview of bonding, reactivity, and mechanistic insights on iodine(III) reactions such as α‐functionalization of carbonyl compounds, alkynylation, amination, CH functionalization, phenol dearomatization, and trifluoromethylation have been described. In keeping with the current practices in mechanistic studies, we have maintained an interdisciplinary flavor in this compilation by providing a balanced view of computational and experimental understanding on the burgeoning domain of hypercoordinate iodine mediated reactions and catalysis. WIREs Comput Mol Sci 2017, 7:e1299. doi: 10.1002/wcms.1299 This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis
(a) Important iodoarene reagents and catalysts used in phenol dearomatization reactions. (b) General representation of phenol dearomatization. (c) Associative and dissociative pathways. (d) Phenol dearomatization involving iodono intermediate. (e) Phenol dearomatization using tartarate derived hypercoordinate iodine reagent 15.
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(a) Phenyliodonium bis‐trifluoroacetate (PIFA) promoted CH functionalization of anilide derivative to form spiro bis‐oxindole. (b) Important mechanistic pathways for the conversion of anilide to mono‐oxindole. Gibbs free energies of stationary points in kcal/mol are given in parentheses. (c) Optimized geometries of important stationary points. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) C6F5I(TFA)2 mediated CH functionalization of alkane and benzene. (b) Relative enthalpy profile in kcal/mol for CH functionalization of ethane. Distances are given in Å.
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Mechanism of amination in (a) methylstyrene, and (b) methylstilbene using iodosobenzene bis‐sulfonimide PhI(NMs2)2. Free energies associated with each stationary point are given in kcal/mol. (c) Optimized geometries of the important transition states (TSs) for different alkene amination. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) Amination reaction of different alkenes with hypercoordinate iodine(III) reagent. (b) Gibbs free energy profile (in kcal/mol) for the diamination of styrene.
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(a) Iodoarene catalyzed stereospecific intramolecular sp3 CH amination. (b) Mechanistic possibilities and (c) optimized geometries of important transition states. Relative free energies (in kcal/mol) of stationary points are given in parentheses. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) 1,1‐Hydrocarboxylation of alkynyl beniodoxole catalyzed by Pd(II), (b) free energy profile (in kcal/mol), and (c) optimized geometries of important transition states for 1,1‐hydrocarboxylation. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) Alkynylation of indoles using tri‐isopropylsilyl‐ethynylbenziodoxolone (TIPS‐EBX) catalyzed by AuCl. (b) Gibbs free energy (in kcal/mol)profile. (c) Optimized geometries of important stationary points. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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Relative Gibbs free energy profile (in kcal/mol) for alkynylation of (a) benzyl thiol and (b) thiophenol using tri‐isopropylsilyl‐ethynylbenziodoxolone (TIPS‐EBX). (c) Optimized geometries of important transition states for the alkynylation of thiophenol. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) Common hypercoordinate iodine reagents used for alkynylation reactions, (b) alkynylation of thiols using ethynylbenziodoxolone (EBX), and (c) possible mechanisms for alkynylation of thiols.
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(a) Relative Gibbs free energy profile (in kcal/mol) for α‐tosyloxylation of acetophenone using Koser's reagent. (b) Optimized geometries of important transition states (TSs) for α‐tosyloxylation of propiophenone. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) Generation of hypercoordinate iodine catalyst 6 by the oxidation of chiral iodooxazoline pre‐catalysts 5 for α‐tosyloxylation reaction. (b) Protonation of hypercoordinate iodine catalyst 6 to give 7. (c) Optimized geometries of cationic intermediates 6′ and 7′ without the tosylate counter ion. Only selected hydrogen atoms are shown for better clarity. Distances are given in Å.
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(a) Effect of different substituents on the catalytic activity of iodoaryl in α‐tosyloxylation. (b) Effect of different substituents on dihedral angle θ(C1–C2–I3–O4). (c) Formation of iodono intermediate 4 and the related ∆Grxn.
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(a) General representation of α‐tosyloxylation ketone catalyzed by Koser's reagent. (b) General mechanism for the α‐tosyloxylation ketone. (c) Commonly employed iodoarenes in α‐tosyloxylation.
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Molecular orbital (MO) diagram for three‐center–four‐electron (3c–4e) bond in hypercoordinate iodine compound RIL2.
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(a) Representative trifluoromethylation reactions using Togni's reagent 1. (b) General representation of different reaction modes of Togni's reagent. Mechanism of trifluoromethylation of (c) terminal olefins catalyzed by Cu(I) and (d) pentanol catalyzed by Zn(NTf2)2.
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(a) Common hypercoordinate iodine reagents used for electrophilic trifluoromethylation. (b) Ritter‐type reaction for NCF3 bond formation using reagent 1. (c) The proposed mechanism. (d) Nucleophilic substitution (SN), reductive elimination (RE), and single electron transfer (SET) mechanism considered for the trifluoromethylation reaction.
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